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SECTION A:
Outlines of the Chemistry of the First Row
Transition Metals
1.1
TITANIUM: Group IV
1.1.1
6320 ppm of the earths crystal rocks, 9th most abundant element, 2nd of the transition
metals.
Abundance:
Ores:
Extraction:
Titanium is difficult to extract because of its high melting point and because it reacts
readily with air, oxygen, nitrogen and hydrogen at high temperatures. Three problems
that have to be surmounted in the preparation of titanium are
it forms carbides which cannot be easily purified and therefore cannot be reduced
with C or CO,
reduction with highly electropositive metals like Na, Ca, or Mg cannot remove all
the oxygen completely and
Ti is extremely reactive at high temperatures and can easily be contaminated with
oxygen and nitrogen, except if prepared in the absence of air.
The scheme below provides two possible routes to the production of TiO2, from which pure titanium
metal can be obtained.
Ilmenite
Rutile
Sulphate cake
Crude TiCl4
Treat with H2S or oil to
reduce the volatile TiCl4
TiCl4
FeSO4 + TiOSO4
FeSO47H2O
(copperas)
Filter
Base pigment
TiOSO4
Boil to hydrolyse and then
seed to produce anatase or
rutile as desired
TiO2xH2O
Wash, then calcine at
800-900C
Base pigment
Sulphate process
Chloride process
Ti + 2MgCl2
TiCl4 + 2Mg 950
4
The MgCl2 and excess of Mg are removed by leaching with water and dilute HCl or by vacuum
distillation leaving titanium sponge which, after grinding and cleaning with aqua regia (1:3 mixture
of concentrated HNO3 and HCl), is melted under argon or vacuum and cast into ingots.
The van Arkel-de-Boer method
This method can be used to purify Ti. Ti is heated in vacuum with I2 to form TiI4, which volatilises.
The gaseous TiI4 is decomposed on a white-hot tungsten filament.
50-250C
1400C
TiI4
Impure Ti + 2I2
Ti + 2I2
W filament
Uses
Titanium is very hard, high melting (1667C), stronger and much harder than steel, better corrosionresistant than stainless steel and good conductor of heat and electricity.
Ti metal and its alloy with Al are therefore used in the aircraft industry in jet and gas turbine engines
and in airframes.
It is also used in marine equipment and in chemical plant.
1.1.2
CHEMICAL PROPERTIES
Its electronegativity is 1.5, more than Group II and III metals but less than those of p-block elements.
Ti is therefore relatively electropositive but less so than metals of Groups II and III.
It reacts directly with most non-metals at high temperature and actually burns in N2.
It is pyrophoric when finely divided but inherently unreactive in the massive form and
Is resistant to corrosion at room temperature because of the formation of a protective oxide film.
Oxidation states:
2TiCl3 heat
TiCl4 + TiCl2
2TiCl2
TiCl4 + Ti
1.1.3
CHEMICAL PROPERTIES
+IV STATE
Oxides
TiO2 is a very important industrial chemical and used mainly as a white pigment in paint and as an
opacifier to make coloured paints opaque.
It has replaced traditional white pigments like (2PbCO3Pb(OH)2), BaSO4 and CaSO4.
The advantages of TiO2 over lead are:
It covers better
It is non-toxic
It does not blacken, if exposed to H2S.
Other uses of TiO2 are for whitening paper, filter in plastics and rubber, delustering and whitening nylon. Rutile is
usually coloured and pure TiO2 can be obtained by two processes, namely, sulphate process and chloride process.
Typical equations involved in the chloride process are:
C
2TiO2 + 3C + 4Cl2 950
H2O
nH2O
conc.
KOH
K2TiO3
TiOSO 4
titanyl sulphate
oxotitanium(IV) sulphate
1.1.4
H2O
nH2O
potassium titanate
(potassium trioxotitanate(IV)
HALIDES
The tetrahalides are the most important; all 12 of which are well characterised.
Compound
TiF4
TiCl4
TiBr4
TiI4
Colour
white
colourless
orange
dark brown
M.p./C
284
-24
38
155
B.p./C
136.5
233.5
377
As the anions become larger they become more polarizable and more easily oxidised by the
small, highly polarising TiVI cation.
As polarisation increases from F- to I-, the tetrahalides become progressively more covalent,
hence:
Melting points/boiling points increase from TiCl4 to TiI4 (Note that because they are all covalent,
m.p./b.p. increase with increase in formula mass);
The m.p. of TiF4 is exceptionally high because of the large electronegativity difference between
Ti and F which makes TiF4 to be predominantly ionic.
TiF4
TiCl4
TiBr4
TiI4
by reaction of HF on TiCl4
by passing Cl2 over the heated TiO2 in the presence of a reducing agent, e.g. C
as for TiCl4 but by passing Br2 over TiO2
by the iodination of the dioxide with aluminium triiodide at ~130.
Write balanced equations for each of the reactions used for the preparation of TiX4.
The tetrahalides are readily hydrolysed, although TiF4 is more stable than the others and the
intermediate oxohalides may be isolated under careful conditions:
2O
2O
TiX4 H
TiOX2 H
TiO2nH2O
The tetrahalides form adducts, TiX4L or TiX4L2, which are crystalline solids that are often soluble in
organic solvents. The adducts are generally polymeric, usually via formation of dimers: TiCl4OPCl3
exists as [TiCl4(OPCl3)]2 with bridged Cl.
Cl
Cl
Ti
Cl
OPCl3
Cl
Cl
Cl
Ti
Cl
OPCl3
Cl
TiCl4 reacts with alcohols and amines to form alkoxides and dialkylamides (solvolytic reactions):
TiCl4 + 4ROH + 4R'NH2 Ti(OR)4 + 4RNH3Cl
TiCl4 + 4LiNEt2 Ti(NEt2)4 + 4LiCl
TiCl4 is used to produce Ziegler-Natta catalyst for the polymerisation of ethene and is the starting
material for the production of most of the commercially important organic titanium compounds.
A solution of TiCl4 and AlEt3 in hydrocarbon zolvent produces a solid which was found by Ziegler and
Natta to catalyse the polymerisation of ethene to polythene.
Cl
Ti
Cl
Cl
surface
Cl AlEt
3
(a) Cl
Et
Ti
Cl
Cl C H
2 4
(b) Cl
CH3
CH2
Cl
Ti CH2
CH2
Cl
Cl
CH3
CH2
CH2
CH2
Cl C H
2 4
Ti
CH3
CH2 CH2
Cl
Ti CH2
Cl
(c) Cl
Cl
Cl
CH3
CH2
CH2
CH2
Cl
Ti CH2
CH2
Cl
1.1.4
COMPOUNDS OF OXOANIONS
Because of the small size and high charge in TiVI titanium at this oxidation state is strongly hydrolysed in
water to yield basic, hydrolysed species such as titanyl sulphate, TiOSO4.
Oxidation state III, d1
Most of the complexes of titanium(III) are octahedral and are made by reacting TiCl3 with excess of the
ligand, giving rise to compounds of the type [TiL6]X3, [TiL4X2]X, [TiL3X3] and (MI)3[TiX6]; (L = neutral
unidentate ligand, X = singly charged anion).
Aqueous solutions of the [Ti(H2O)6]3+ ion are obtained by reducing aqueous TiIV either electrolytically or
with zinc. The hexaaqua ion is violet in colour and the ion can reduce O2. The solution must therefore be
handled under N2 or H2.
Differently coloured hydrates are known, corresponding to different isomers:
[Ti(H2O)6]3+(Cl-)3
[Ti(H2O)5Cl]2+(Cl-)2
- violet
- green
1.2
VANADIUM
1.2.1
Atomic Number:
23
II III *IV V
* The most important oxidation state
Abundance:
136 ppm of the earths crystal rocks; 19th most abundant element, 5th most abundant transition
element after Fe, Ti, Mn and Zr.
Ores:
Patronite, VS4; vanadinate (lead chloride vanadate), PbCl23Pb3(VO4)2, and carnotite (potassium
uranyl vanadate), K(UO2)(VO4)1.5H2O mainly.
Also found associated with petroleum, particularly from Venezualan and Canadian crudes.
Oxidation states
+II and +III states are reducing, +IV is stable and +V is slightly oxidising.
1.2.2
CHEMICAL PROPERTIES
OXIDES
+V
+IV
+III
+II
V2O5
VO2
V2O3
VO
yellow
deep-blue
Green?
Grey-black
heat
2NH4VO3
V2O5 + 2NH3 + H2O
V2O5 is amphoteric, but mainly acidic.
It reacts with strong NaOH to give oxovanadate(V) ions, VO 34 .
It dissolves in acids to give pale yellow dioxovanadium(V) ion, [VO2]+.
VO2+ + 2H+ + e VO2+ + 2H2O
E = 1.0 V
VO43- + H2O [VO3(OH)]2- + OHpK = 1.0
Some reactions of V2O5 are:
V2O5 + NaOH various vanadates
peroxovanadates (red colour)
V2O5 + H2O2
2VOCl3 + 1O2
V2O5 + 3Cl2
2VO2 + SO3
V2O5 + SO2
2VO2 + V2O3 + 3H2O
2V2O5 + 3H2
VO2 is amphoteric but more basic than acidic.
It forms blue solutions of oxovanadium(IV) ion, VO2+, in acids.
Numerous oxovanadium(IV) compounds are known, VOSO4 being the most important.
9
1.2.3
OXOVANADIUM IONS
Reduction from VV to VIV can readily be done by reacting the solution of vanadate(V) salt with SO2(g) (hot
acidified Na2SO3) while reduction through to +II state requires a stronger reducing agent like Zn/Hg.
Changes in oxidation state are shown by changes in colour.
VO 2
VIII
VII
SO
2 VO2+
Orange yellow
blue
green
deep blue
Zn/Hg
1.2.4
HALIDES
Fluorides
Chlorides
Bromides
Iodides
+5
VF5
+4
VF4
VCl4
VBr4
+3
VF3
VCl3
VBr3
VI3
+2
VF2
VCl2
VBr2
VI2
Note:
10
1.3
CHROMIUM
1.3.1
Atomic Number:
24
II *III IV V VI
* The most important oxidation state
Electronegativity: 1.6
Abundance:
Ores:
Preparations of chromium
Chromium is produced in two forms
(a)
As ferrochrome by the reduction of chromite with coke in an electric arc furnace. The
iron/chromium alloy is used directly as an additive to produce chromium-steels which are
stainless and hard;
(b)
As chromium metal by the reduction of Cr2O3. This is obtained by aerial oxidation of chromite
in molten alkali to give sodium chromate, Na2CrO4, which is leached out with water, precipitated
and then reduced to the chromium(III) oxide by carbon or aluminium (alumino-thermic process)
or silicon:
Cr2O3 + 2Al 2Cr + Al2O3
2Cr2O3 + 3Si 4Cr + 3SiO2
1.3.2
COMPOUNDS
OXIDES
+VI
CrO3
+IV
CrO2
+III
Cr2O3
CrO3
CrVI is very small and the oxide is therefore strongly acidic and covalent.
M.p. is 197C.
Deep-red crystals made up of chains of corner-shaped CrO4 tetrahedra.
It is commonly called chromic acid and is prepared by the addition of concentrated H2SO4 to a
saturated aqueous solution of a dichromate.
It is a strong oxidising agent, very useful in organic synthesis.
On strong heating (220-250C) it loses oxygen to give a succession of lower oxides until the green
Cr2O3 is formed.
11
Cr2O3 is amphoteric.
It is the most important/stable oxide of Cr. I
t is used mainly as a green pigment.
It is the final product of combustion of Cr.
It is more conveniently prepared by heating ammonium dichromate.
(NH4)2Cr2O7 Cr2O3 + N2 + 4H2O
Cr2O3 is unreactive when produced by dry method, but if precipitated as the hydrous oxide (or
hydroxide) from aqueous chromium(III) solutions it is amphoteric.
It dissolves readily in aqueous acids to give an extensive cationic chemistry based on the [Cr(H2O)6]3+
ion and in alkalis to produce complicated, extensively hydrolysed chromate(III) species.
1.3.3
Cr2O3
+ 6H (aq)
+ 3H2O
2Cr 3(aq)
Cr2O3
+ 3OH-
Cr(OH)3 Cr2O3(H2O)n
HALIDES
Anhydrous Cr2+ halides are obtained by action of HCl, HBr or I2 on the metal at 600-700C or by
reduction of the trihalides with H2 at 500-600C
CrCl2 dissolves in water to give a blue solution of the Cr2+ ion.
CrCl3 is made by reacting SOCl2 with hydrated chloride.
CrCl3 forms adducts with donor ligands.
+6
+5
+4
+3
+2
Fluorides
CrF6
CrF5
CrF4
CrF3
CrF2
Chlorides
Bromides
Iodides
CrCl4
CrCl3
CrCl2
CrBr4
CrBr3
CrBr2
CrI4 ?
CrI3
CrI2
Note:
The group oxidation state of +6 and +5 are attained only with strongly oxidising fluorine.
At +4 state the iodide has a doubtful existence.
In the lower oxidation states all the halides are known.
12
The trihalides are made by reacting the halogen and the metal, though CrF3 is better obtained by reacting
HF and CrCl3 at 500C.
CrCl3 is rather insoluble in water but dissolves if the water contains traces of reducing agent. The reducing
2 in solution
agent produces some Cr2+ ions. Dissolution follows as a result of electron transfer from Cr (aq)
1.3.4
The Cr2+ ion is very unstable to air and most of its chemistry has to be handled under N2 or Ar. It reduces
water to liberate H2.
[Cr(H2O)6]2+ can be produced by electrolytically reducing Cr3+ or by reducing with zinc amalgam. Its
colour is sky blue. It is one of the strongest reducing agent known in aqueous solution.
2
Cr (aq)
+ e, E = 0.41 V
Cr 3(aq)
2+
Cr is used to remove the last traces of O2 in N2. The ion is usually stabilised by forming complexes, e.g. [Cr(NH3)6]2+.
1.3.5
There are thousands of chromium(III) complexes. Most of the complexes are octahedral. Chromium(III)
complexes are inert in aqueous solutions. [Inert complexes do not undergo substitution readily].
The hexaaqua ion, [Cr(H2O)6]3+, occurs in many salts, such as violet [Cr(H2O)6]Cl3 and alums,
MICr(SO4)212H2O. [Cr(H2O)6]Cl3 exists in three isomers, the others being trans-[CrCl2(H2O)4]Cl 2H2O
(dark green) and [Cr Cl(H2O)5]Cl2 H2O (pale green).
The hexaaqua ion hydrolyses in water to give an acidic solution and an hydroxo ion. The hydroxo ion
condenses to give a dimeric hydroxo bridged species:
4+
[Cr(H2O)6]3+ + H2O
-H+
+H+
OH
[Cr(H2O)5OH]2+ + H3O+
(H2O)4 Cr
Cr (H2O)4
OH
At pH>6 CrO3 forms the tetrahedral yellow chromate ion, CrO 24 . Between pH 2 and 6, HCrO 4 and the
orange yellow dichromate ion, Cr2O 72 , are in equilibrium. At pH<1 the main species is H2CrO4:
HCrO 4 CrO 24 + H+
H2CrO4 HCrO 4 + H+
Cr2O 72 + H2O 2HCrO 4
13
K = 10-59
K = 4.1
K = 10-22
O
O
O
Cr
Cr
Cr
O
O
O
2-
2-
Cr2O 4
Cr2O 7
Sodium dichromate, Na2Cr2O7.2H2O is commercially the most important compound of chromium. It yields a wide
variety of pigments used in the manufacture of paints, inks, rubber and ceramics and from it are formed other chromates
used as corrosion inhibitors and fungicides, etc. It is also used as oxidant in many organic chemical processes.
Acidified dichromate solutions are used as strong oxidant in volumetric analysis:
Cr2O 72 + 14H+ + 6e 2Cr3+ + 7H2O;
E = 1.33 v
K2Cr2O7 is preferred in volumetric analysis, because it is not hygroscopic like the sodium salt and is
often used as primary standard.
14
1.4
MANGANESE
1.4.1
Atomic Number:
25
occurs primarily in silicates. Most important secondary deposits are pyrolusite, MNO2,
(most important, hausmannite, Mn3O4 and rhodochrosite, MnCO3. The secondary
deposits are products of weathering of the primary source. SA is the second largest
producer of Mn after USSR. 1600 ppm 12th most abundant element.
Electronegativity:
Reactivity:
II III IV V VI VII
1.5
Mn is more electropositive than any of its neighbours in the PT and the metal is more
reactive.
1.4.2
COMPOUNDS
OXIDES
+VII
Mn2O7
Mn2O7
MnO2
+VI
+V
+IV
MnO2
+III
Mn2O3
Mn3O4
+II
MnO
15
Fusion of MnO2 with an alkali metal hydroxide and an oxidising agent such as KNO3 produces very darkgreen mangante(VI) salts, which are stable in strongly alkaline solutions but which disproportionate readily
in neutral or acidic solution:
3 MnO 24 + 4H+ 2 MnO 4 + MnO2 + 2H2O
Mn2O3
Mn3O4
MnO
basic and ionic and is obtained by reduction of any oxide of manganese by hydrogen gas.
1.4.3
HALIDES
+7
+6
+5
+4
+3
+2
Fluorides
Chlorides
Bromides
Iodides
MnF4
MnF3
MnF2
MnCl2
MnBr2
MnI2
Note the tendency of Mn not to form halides at high oxidation states, not even with fluorine.
MnF4 is the highest halide formed by Mn. Prepared by reacting the elements.
MnF3 is a red-purple, reactive, but thermally stable solid. Prepared by fluorinating any of the MnII
halides.
They are pale-pink salts obtained by dissolving the metal or carbonate in aqueous HX.
MnF2 is insoluble in water and forms no hydrate, but the others form a variety of very
water-soluble hydrates.
Tetrahydrates are the most common.
Manganese(II), d5
Manganese(II) salts are generally water-soluble. Additions of OH- ions to Mn2+ solution gives the
gelatinous white ppt. The hydroxide rapidly darkens in air due to oxidation.
0.2 v
v
MnO2 0.1
Mn2O3
Mn(OH)2
Mn(II) complexes are generally unstable because the ion has no ligand field stabilisation energy. However,
chelating ligands do form stable complexes.
Manganese(III), d4
16
MnIII has a high tendency to hydrolyse and to disproportionate in weakly acidic solution.
2Mn3+ + 2H2O Mn2+ + MnO2 + 4H+ K 109
Manganese(III) acetate will oxidise alkenes to lactones and toluene to phenol. Mn(III) and Mn(IV)
complexes are important in photosynthesis, where the oxygen evolutions depends on manganese.
Manganese(VI), d1 and manganese (VII)
Mn(VI) is found in MnO 24 (deep green colour), which is formed by oxidising MnO2 in fused KOH with
KNO3 or air. The ion is stable only in very basic solutions.
In acid, neutral, or slightly basic solutions it disproportionates:
3MnO 24 + 4H+ 2MnO 4 + MnO2 + 2H2O
Mn(VII) is best known in permanganates, MnO 4 . KmnO4 is manufactured by electolytic oxidation of a
basic solution of K2MnO4. MnO 4 is purple. It can be produced in solution by oxidising MnII salts with
very powerful oxidising agents such as PbO2 or NaBiO3.
Solutions of MnO 4 are unstable, decomposing slowly but rapidly in acidic solution:
4MnO4- + 4H+ 3O2(g) + 2H2O + 4MnO2(s)
In neutral or slightly alkaline solutions when kept in the dark, decomposition is very slow. The
decomposition is catalysed by light so standard permanganate solutions should be stored in dark bottles.
In basic solution, 4MnO 4 is a powerful oxidant:
MnO4- + 2H2O + 3e MnO2 + 4OH- E = 1,23 v.
In very strong base and with excess of MnO 4 , manganate(VI) ion is formed:
MnO4- + e MnO 24
E = 0,56 v.
In acidic solution MnO 4 is reduced to Mn2+ by an excess reducing agent:
MnO4- + 8H+ + 5e Mn2+ + 4H2O
E = 1,51 v.
If excess MnO4- is present the Mn2+ is re-oxidised:
2MnO 4 + 3Mn2+ + 2H2O 5MnO2 + 4H+.
i.e. the product of the reaction between and a reducing agent in the presence of excess MnO 4 is MnO2(s).
Reaction between KMnO4 and concentrated H2SO4 gives Mn2O7:
2KMnO 4 + 3H2SO4 2K+ + Mn2O7 + H3O+ + 3HSO4.
Recall that Mn2O7 is dangerously explosive.
17
1.5
IRON
1.5.1
Atomic Number:
26
II* III* IV V VI
*
Most important.
Electronegativity:
1.8
Abundance:
Iron is the second most abundant metal after Al and the fourth most abundant element in the earths
crust. The core of the earth is believed to consist mainly of Fe and Ni. The major ores are haematite,
Fe2O3; magnetite, Fe3O4; Pimonite, FeO(OH); and siderite, FeCO3. Abundance is 62000 ppm.
Reactivity:
1.5.2
IRON COMPOUNDS
1.5.3
BINARY COMPOUNDS
OXIDES
Only FeO and Fe2O3 are known. They are both basic, with FeO being more basic.
FeO is usually non-stoichiometric, Fe0.95O, which means that some FeIII is present in FeO. It is pyrophoric
and can be obtained by heating iron(II) oxalate. The oxide is black.
Fe2O3 is brown. Occurs naturally. Otherwise can be made by ignition of hydrated iron(III) oxide,
precipitated from iron(III) solution by ammonia.
Fe3O4 is black. Occurs naturally as magnetite. It is the ultimate product of strong ignition in air of the
other two oxides. It is better written as FeIIFe III
2 O4 or FeO.Fe2O3.
HYDROXIDES
Addition of an alkali solution to Fe2+ gives a pale green hydroxide, which is very readily oxidised by air to
give red-brown hydrous iron(III) oxide.
18
Fe(OH)2 is a true hydroxide and is somewhat amphoteric. It dissolves in hot concentrated NaOH to give
blue crystals of Na4[FeII(OH)6].
Additions of OH- ions to iron(III) solutions gives a red-brown gelatinous mass commonly called iron(III)
hydroxide, but is best described as a hydrous oxide, Fe2O3nH2O. Rust is hydrated iron(III) oxide.
1.5.4
HALIDES
+3
+2
Note:
1.5.5
Fluorides
FeF3
FeF2
Chlorides
FeCl3
FeCl2
Bromides
FeBr3
FeBr2
Iodides
FeI2
Fe(II) is the most stable and exists in aqueous solution. Fe(III) is slightly oxidising.
Iron(II), d6
The iron(II) ion, [Fe(H2O)6]2+, gives many crystalline salts. Mohrs salt, (NH4)2[Fe(H2O)6](SO4)2 is reasonably
stable toward air and less of water. It is therefore used as primary standard for solutions of Fe2+ for volumetric
analysis. FeSO47H2O slowly effloresces and turns brown-yellow when kept in air. Fe2+ hydrolyses.
Octahedral complexes are generally paramagnetic.
diamagnetic, e.g. [Fe(CN)6]4-.
Iron(III), d5
Iron(III) occurs in crystalline salts with most anions, except I- (why?).
Iron(III) salts containing [Fe(H2O)6]3+, e.g. Fe(ClO4)310H2O, are pale-pink to nearly white and the aquo
ion is pale purple. Unless Fe3+ solutions are strongly acid hydrolysis occurs and the solutions are
commonly yellow because of formation of hydrous species (charge-transfer bands).
[Fe(H2O)6]3+ + H2O [Fe(H2O)5OH]2+ + H3O+
[Fe(H2O)5OH]2+ + H2O [Fe(H2O)4(OH)2]+ + H3O+
The hexacyanoferrate(III) ion, [Fe(CN)6]3-, in contrast to hexacyanoferrate(II) ion, [Fe(CN)6]4-, is quite
poisonous because the CN- ions rapidly dissociate, whereas [Fe(CN)6]4- is not labile.
1.5.6
Iron is essential in small amounts for plants and animals. It is, however, toxic in large quantities.
Biologically iron is the most important transition metal. It is involved in the following:
20
1.6
COBALT
1.6.1
Atomic Number:
27
Abundance:
29 ppm, widely distributed but is 30th most abundant element and is less common than all other
transition metals except Sc (25 ppm). The more important of the ores are arsenides and sulphides:
smaltite, CoAs2, cobaltite (or cobalt glance), CoAsS and linnaeite, Co 3S4. These ores are often
associated with nickel, copper and lead and are usually obtained as by-products or co-product in the
recovery of these metals. Main producers are: Zaire (22%), Canada (17%), Zambia (15%), USSR
(15%) and Australia (9%).
Oxidation states
+II and +III are the most important. Co2+ is more stable than Co3+. The hydrated ion [Co(H2O)6]2+
exists in simple salts and is stable in water. Simple salts of Co3+, however, are oxidising and are
relatively unotable. Co3+ is stable and is very important in complexes.
1.6.2
Cobalt is relatively unreactive, although it slowly dissolves in dilute mineral acids. It does not react
with H2O, H2, or N2, though it reacts with steam to form CoO. Like iron it is rendered passive by
concentrated HNO3. Co combines readily with the halogens.
Chemistry of +II state, d7
CoII is the most important for simple salts of Co (though +III state is the most important for
complexes).
CoO and Co(OH)2 and simple salts of the common acids such as CoCl2, CoBr2, CoSO4, Co(NO3)2 and
CoCO3 are known.
The hydrated salts are pink or red and contain [Co(H2O)6]2+. Most cobalt(II) salts are soluble in water
except CoCO3.
Addition of OH- to Co2+ gives the hydroxide which may be blue or pink, depending on the conditions;
it is weakly amphoteric dissolving in very concentrated OH- to give a blue solution containing the
[Co(OH)4]2- ion.
Co2+ forms many complexes which are less stable than Co3+ complexes.
Most common complexes of cobalt(II) are tetrahedral or octahedral.
A melt of CoO with SiO2 and K2CO3 gives a deep blue glass potassium cobalt(II) silicate.
21
Commercially this blue glass is ground into powder (called smalt) and used as a pigment to give a blue
colour to glass, enamels and glazes.
In the laboratory, cobalt glass is used in flame test for potassium in the presence of sodium. The blue
glass absorbs the intense yellow colour from sodium.
CoCl2 is used to test for water, both as cobalt chloride paper and as an indicator added to silica gel.
CoCl26H2O is pink and contains octahedral [Co(H2O)6]2+ ions. If this is partially dehydrated by heat
the colour changes to blue of the tetrahedral ions, [Co(H2O)4]2+. Addition of water restores the pink
colour:
[Co(H2O)6]2+ [Co(H2O)4]2+ + 2H2O
pink
blue
If [Co(H2O)6]2+ is evaporated in the presence of chloride ion the equilibrium is:
[Co(H2O)6]2+ + 4Cl- [Co(Cl)4]2- + 6H2O
pink
blue
CoX2 (X = F, Cl, Br, I) are known. CoF2 (pink), CoCl2 (blue), CoBr2 (green) and CoI2) (blue-black).
+III state, d6
Simple compounds of Co(III) are few, e.g. Co2(SO4)318H2O, NH4Co(SO4)212H2O. These salts are
blue and contain [Co(H2O)6]3+ ions. They are all strongly oxidising.
Co2O3 is known as the hydrated oxide which can oxidise water. Of the halides only CoF3 is known
and it is readily hydrolysed in water. The coordination chemistry of Co3+ is vast.
Almost all Co3+ complexes are octahedral. They are synthesised by oxidation of Co2+ in solution in
the presence of the ligands. O2 or H2O2 and a catalyst, such as activated charcoal, are used, e.g.
4[Co(NH3)6]3+ + 2H2C
4Co2+ + 4NH 4 + 20NH3 + O2 charcoal
Co3+ ion has affinity for N donors, such as NH3, cn, adta and NCS-.
The study of cobalt(III) complexes has contributed to the development of coordination chemistry.
Vitamin B12 is an important complex of Co, used in the treatment of anti-pernisious annemia.
22
1.7
NICKEL
1.7.1
Atomic Number: 28
Electronic configuration: [Ar]3d84s2
Oxidation states: II* III IV
*
Most important.
Electronegativity:
1.8
Abundance:
99 ppm. Seventh most abundant transition and twenty-second most abundant element in the earths crust.
Commercially important ores are:
Laterites: oxide/silicate ores such as garnierite, (Ni, Mg)6Si4O10(OH)8 and nickeliferous limonite,
(Fe, Ni)O(OH)nH2O, which are concentrated by weathering.
Sulphides such as pentlandite, (Ni, Fe)9S8, associated with copper, cobalt and precious metals.
(Ore contains ~1% Ni). Found in Canada and South Africa.
The remaining sulphide malte is cooled slowly giving an upper layer of Cu2S and a lower layer of
Ni2S3 separated mechanically.
NiO and water gas (H2 + CO) are warmed at 50 under atmospheric pressure. The H2 reduces
NiO to Ni, which in turn reacts with CO to give volatile [Ni(CO)4] toxic and inflammable.
Heating the gas to 230C the compound decomposes and the CO is recycled.
50
Dissolves readily in dilute acids to give [Ni(H2O)6]2+ concentrate and H2. Rendered passive by
concentrated HNO3 and aqua regia.
Ni has capacity to absorb hydrogen when finely divided Raney nickel is used as catalyst.
It is therefore
COMPOUNDS OF NICKEL
Oxidation state of +II is the most important. Ni, Co and Fe are ferromagnetic.
NiO
Cannot be prepared pure by reacting with O2. It is prepared by heating Ni(OH)2, NiCO3 or Ni(NO3).
It is entirely basic. Green powder.
23
Ni(OH)2
Ni(OH)2 is precipitated (as green) when OH- ions are added to aqueous solution of Ni2+ salts. It is also
entirely basic.
NiX2
(X = F, Cl, Br, I). No other halide is known, except NiF2, which can be obtained from the elements.
NiF2 is obtained by reacting F2 with NiCl2 at 350C. NiF2 is slightly soluble in water while the other
halides are soluble to give [Ni(H2O)6]2+ ions.
1.7.3
Ni(II) COMPLEXES
Octahedral complexes
The commonest six-coordinate complex is the green aqua ion, [Ni(H2O)6]2+ which is formed when Ni,
NiCO3, Ni(OH)2, etc. react with acids and give salts like NiSO47H2O or NiCl26H2O.
The water molecules in the aqua ion can be readily displaced, by ammonia, for example, to give trans[Ni(H2O)2(NH3)4]2+ or [Ni(NH3)6]2+. Ni(en)3]2+ can also be formed if en is used. These complexes are
blue or purple because of shifts in absorption bands when H2O is replaced by a stronger field ligand.
Four-coordinate complexes
Four-coordinate complexes can be square planar or tetrahedral. Most 4-coordinate complexes of
nickel are square planar and red (in most cases). All the d8 ions of Ni2+ in square-planar complexes are
paired and the complexes are therefore diamagnetic.
A good example is bis(dimethylglyoximato)nickel(II), [Ni(dmgH)2]
H
H3C
CH3
C
C
Ni
C
H3C
CH3
The formation of this complex quantitatively is used in gravimetric determination of nickel. It is precipitated
on addition of ethanoic dmgH2 to ammoniacal nickel(II) solution. [Ni(CN)4]2- is also square planar.
Tetrahedral complexes
Tetrahedral complexes are less common than planar complexes and are all paramagnetic. The
complexes are of the type [NiX4]2-, [NiX3L]-, [NiX2L2] and [Ni(L-L)2], where X is halide ion, L is a
neutral ligand (e.g. R3P or R3PO) and L-L is bidentate uninegative ligands.
Five coordinate complexes
They are either trigonal bipyramidal or square pyramidal. They are paramagnetic.
We shall discuss the conformational properties of nickel next year.
24
1.8
COPPER
1.8.1
Atomic Number:
29
I *II III
* The most important oxidation state
Electronegativity:
Abundance:
Ores:
1.9
Most common ore is chalcopyrites, CuFeS2; copper glance (chalcocite), Cu2S; cuprite, Cu2O and
malachite, Cu2CO3(OH)2.
The sulphide ores are crushed and concentrated by froth-floatation, roasted and reduced:
O2
2CuFeS2
Cu2S + Fe2O3 + 3SO2
1400-1450
Sand is added to remove iron as iron silicate slag, Fe2(SiO3)3.
2FeS + 3O2 2FeO + 2SO2
FeO + SiO2 Fe2(SiO3)3
Cu2S + O2 Cu2O + SO2
The Cu2O is reduced by self-reduction by the sulphide
2Cu2O + Cu2S 6Cu + SO2
The copper formed is impure and known as blister copper (98-99% pure).
The blister copper is purified by electrolysis using Cu electrodes with the electrolyte of dilute H2SO4 and
CuSO4. The impure blister copper is made the anode.
1.8.2
Cu is stable to dry at room temperature but forms Cu2O at red heat. Cu is also attacked by S and
halogens. When Cu is exposed to an atmosphere containing S, it tarnishes and deposits a green
coating of a basic sulphate.
Cu dissolves in concentrated H2SO4 and on both dilute and concentrated HNO3.
3Cu + 8HNO3(dil) 2NO + 3Cu(NO3)2 + 4H2O
Cu
COMPOUNDS OF COPPER
OXIDATION STATE +1
Most of the simple compounds and complexes are diamagnetic and colourless because the ions have
d10 configuration. Few coloured compounds include Cu2O (yellow or red), Cu2CO3 (yellow) and CuI
(brown). The colour arises from charge-transfer bands.
25
2Cu+ Cu2+ + Cu
[Cu ]2
The equilibrium constant is very high which implies that the equilibrium is far to the right. Thus the
concentration of Cu+ is very low in solution and typically a Cu+ ion exists in aqueous solution for less
than a second.
CuCl, CuCN and CuSCN are insoluble in water and Cu2+ can be estimated gravimetrically as CuSCN:
2Cu2+ + SO 32 + 2SCN- + H2O 2CuISCN + H2SO4
Cu2+ is reduced to copper(I) oxide by mild reducing agents. This is the basis of Fehlings test for
reducing sugars.
Cu2O is a basic oxide and reacts with hydrogen halide acids, HCl, HBr and HI, to give insoluble CuCl,
CuBr and CuI. CuF is unknown.
Addition of KI to a solution of Cu2+ results in the I- ions reducing Cu2+ to CuI and the I- oxidised to I2.
2Cu2+ + 4I- 2CuI + I2
2S2O 32 + I2 S4O 62 + 2ICuX are insoluble in water but dissolve in solutions containing excess of halide ions to form soluble
halide complexes:
CuCl + Cl- [CuCl2]+ 2Cl- [CuCl3]2+ 3Cl- [CuCl4]39
+II Oxidation state, d
+II is the most stable and important oxidation for Cu.
Cu2+ compounds have one unpaired electron. Most of them are therefore paramagnetic.
compounds are also typically coloured due to d-d transition. Many hydrated Cu2+ salts are blue.
The
CuO(black) is obtained by heating oxosalts like Cu(NO3)2, CuCO3 or Cu(OH)2. Addition of OH- ions
to Cu2+ solution gives a blue ppt. If aqueous ammonia is used a pale blue ppt is formed which
dissolves in excess ammonia to give a deep blue solution.
Aqueous Cu2+ solutions form many complexes with ammonia and amines, such as [Cu(H2O)5NH3]2+,
[CuH2O)4(NH3)2]2+, [Cu(H2O)3(NH3)3]2+ and [Cu(H2O)2(NH3)4]. The halide complexes show two
different stereochemistries. In (NH4)2[CuCl4] the [CuCl4]2- ion is square planar, but in Cs2[CuCl4] and
Cs2[CuBr4] the [CuX4]2- ions have a slightly squashed tetrahedral shape.
Tetrahedral [CuCl4]2- ions are orange and square planar.
26
SECTION B
SECOND AND THIRD ROWS
TRANSITION METALS
27
2. THE ELEMENTS OF THE SECOND AND THIRD ROW TRANSITION METAL SERIES.
Comparison of 2nd and 3rd rows with first row
2nd and 3rd row transition metals of a particular group have similar chemical properties but
both exhibit different properties from their 1st row congeners.
There are, however, some similarities, e.g. Rh3+ complexes are
similar to Co3+ complexes.
The atomic and ionic radii of 2nd and 3rd row transition metals of a particular group are
comparable. The filling of the 4f orbitals in the intervening lanthanides between group 3 and
group 4 causes a steady contraction (lanthanide contraction) in atomic and ionic sizes. The
lanthanide contraction offsets differences in sizes, which should occur due to increase in
nuclear charge and principal quantum number.
All the transition metals are known to exhibit variable oxidation states. For the first row
series, the lower oxidation states are generally reducing and dominate the aqueous chemistry,
whereas the higher oxidation states are oxidising and occur as oxo-ions. For the second and
third row series, the higher oxidation states are generally more stable (i.e. not oxidising).
Aquo ions at low/medium oxidation states are generally unknown or poorly defined. Some of
them do form clusters at these oxidation states.
The heavier transition metals are more prone to forming strong M-M bonds than are those in
the first row series, where very few or no M-M bonded species are known.
The 2nd and 3rd row series have magnetic properties which are of little use to chemist than in
the first row.
The tendency to form low-spin complexes is high because of very large crystal field splitting
energy and strong metal-metal bonding.
Those with an even number of electrons are usually diamagnetic while those with an odd
number of electrons usually behave as having one unpaired electron.
2.1
2.1.1
PHYSICAL PROPERTIES
Electronic structure
Titanium
Ti
Zirconium
Zr
Hafnium
Hf
Electron config.
Ar 3d 2 4s2
Oxidation states
(-I),(0),(II),(III) IV*
Kr 4d 2 5s2
Xe4f 14 5d 2 6s2
*Most important oxidation state; others are well characterised but are less important.
Terrestrial abundance of elements
Ti
Minerals:
The 9th most abundant element by weight in the earths crust (63%; 6320 ppm), it is
therefore very abundant. It is the 2nd most abundant metal.
Ilmenite (FeTiO3) and rutile (TiO2).
28
2.5 ppm).
Minerals: It is only in few minerals, such as alvite MSiO4.xH2O (M = Hf, Th, Zr) does the content of
Hf exceed that of Zr.
Because of the lanthanide contraction, the ionic radii of Zr and Hf are virtually identical and their
association in nature parallels their very close chemical similarity. Separation of Hf and Zr is
consequently very difficult.
2.1.2
Uses
Ti
airframes. TiO2 is
Zr
Zr is used for cladding (casing for UO2 fuel in water-cooled nuclear reactors). Zr is corrosionresistant, has high melting point. (1851C) and low absorption of neutrons, hence the use. Zr is
also used to make alloys with steel and a Zr/Nb alloy is an important superconductor.
Hf
Hf is used to make control rods for regulating the free neutron levels regulating the nuclear
reactors used in submarines because Hf has capacity to high absorption of thermal neutrons. Zr
used for cladding must therefore be free of Hf.
Zr
Hf
Atomic number
22
40
72
Electron Config.
Ar 3d 2 4s2 Kr 4d 2 5s2
Metal radius/pm
147
160
159
IV
60.5
72
71
III
67.0
II
86
Xe4f 14 5d 2 6s2
Melting point/C
1667
1857
2222
Size
Covalent and ionic radii increase from Ti to Zr but Zr and Hf have almost identical size. Lanthanide
contraction cancels out the expected size increase from Zr to Hf. The identical size and similar outer
electron configuration make their chemical properties almost identical.
2.1.4
CHEMICAL PROPERTIES
H2SO4 and aqua regia. (Ti dissolves slowly in hot concentrated HCl, giving Ti3+ and H2. Ti is
oxidised by hot HNO3, giving the hydrated oxide, TiO2.(H2O)n.). HF is the best solvent for all metals.
They form soluble fluoro complexes:
M + 6HF H2[MF6] + 2H2
They are reactive at high temperatures (>450), reacting with oxygen, halogens, nitrogen and carbon
to form oxides, MO2, halides, MX4, interstitial nitrides (MN) and carbides (MC) respectively.
The most important oxidation state is +4. Compounds at this oxidation state are covalent because of
the high charge. However, Zr and Hf, being larger, form more basic oxides than that TiO2. The
aqueous chemistry of their compounds is more extensive and the compounds are less hydrolysed.
The MIV ions of Zr and Hf attain coordination numbers of 7, 8 or more, unlike first row transition
elements, because of their larger sizes and high charge.
2.1.5
200
Zr + 2I2 ZrI4 Tungsten or
Zr + I2
zirconium
filament
Separation of Zr and Hf
The similarity in size of ions makes separations exceedingly difficult. Separation exploits the
different solubility of the nitrates. Zr and Hf are separated by solvent extraction of their nitrates into
tri-n-butylphosphate or thiocyanate into methylisobutylketone. Ion-exchange of an alcoholic solution
of the tetrachlorides on silica gel columns followed by elution of the column with an alcohol/HCl
mixture can also be used. The Zr comes off first.
2.1.6
The oxides
The main oxides are the dioxides and TiO2 is by far the most important compound formed by the
elements. ZrO2 and HfO2 are known. TiO2 is not reactive, has a low coefficient of thermal expansion
and a very high melting point (2710 25C). It is therefore a useful refractory material, used in the
manufacture of crucibles and furnace cores. Fibrous ZrO2 is used in weaving fabrics, which can be
used as an insulator and for filtering corrosive liquids. Fibrous ZrO2 is chemically inert, refractive and
apparently non-toxic, hence the use.
Addition of hydroxide to ZrIV solution causes the precipitation of white gelatinous ZrO2.nH2O, with
variable water content. No true hydroxide of Zr exists. On strong heating, this hydrous oxide gives
hard, white, insoluble ZrO2.
TiO2+ and ZrO2+ exist in solution and can form compounds like ZrO(NO3)2 , ZrO(SO4), etc.
TiO2, ZrO2 and HfO2 are all very stable white solids, non-volatile and are rendered refractory by
strong heating. The basic properties of the oxides increase with increase of atomic number: TiO 2 amphoteric; ZrO2 and HfO2 are increasingly basic. TiO2 dissolves in both bases and acids, forming
titanates and titanyl compounds.
TiO SO 4
titanyl sulphate
conc
H 2 SO 4
TiO 2 (H 2 O) n
conc
NaOH
Na 2 TiO 3 (H 2 O) n
sodium titanate
31
The tetrahalides, MCl4 , MBr4 and MI4, are monomer and tetrahedral in the gas phase. The solids are
polymeric with halide bridging:
ZrF4(s) - 8-coordinate (square antiprismatic). On heating to 800 C the vapour is ZrF4
monomer.
ZrCl4(s) - a polymer consisting of zigzag chains of [ZrCl6]2- (octahedral). It sublimes at
331C.
The tetrabromides and tetraiodides have fairly low melting points (bromides: Zr, 450; Hf, 424;
iodides: Zr, 500; Hf, 449) and are volatile.
Can you explain why the melting points of the tetra-iodides are higher that those of tetra-bromides?
Melting points of the halides
M
MF4
MCl4
MBr4
MI4
Ti
284
-24
38
155
Zr
932(903sub)
438
450
500
424
449
Hf
ZrBr4 and ZrI4 are similar to ZrCl4. ZrF4 is a white crystalline solid subliming at 903C; it has an 8coordinate structure. The fluorides are less susceptible to hydrolysis and though an aq HF produces
the oxofluorides, MOF2, the hydrates MF4H2O and MF43H2O are known. These can be crystallised
from HF-HNO3 solutions. The trihydrate has an 8-coordinate structure with two bridging fluorides,
(H2O)3F3ZrF2ZrF3(H2O)3.
F
/ \
[( H 2 O) 3 F3 Zr ZrF3 ( H 2 O) 3 ]
\ /
F
The Hf hydrate has the same stoichiometry but a different structure with chains of HfF4(H2O) units
linked through four bridging fluoride atoms.
F
/ \
\
/ HfF2 (H 2 O) 2 \ /
F
The third water is held in the lattice.
MCl4py2 , MCl4bipy , and MX4(diars)2 (M= Zr, Hf; X= Cl , Br). ZrCl4 reacts with dicarboxylic acids
above 100 to give Zr(RCO2)4 compounds.
The tetrahalides also form complex anions with halides. Fluorozirconates and fluorohafnates, with
coordination number tending to 8, e.g., AMF8 and AMF7 (where A are different counter-ions and M =
Zr, Hf), are known in addition to AMX6 (X = F, Cl, Br). The complex halides may be made by dry or
wet methods, e.g.
ZrF4
HFaq
+ 2KF K2ZrF6
ZrF4
+ KF
fuse KZrF
5
K2HfCl6 + H2O
Other known complexes are Na3ZrF6 (where the anion is 7-coordinate pentagonal bipyramidal),
Li6[BeF4][ZrF8] (the zirconium anion is 9-coordinate, distorted dodecahedral), Cu6[ZrF8]12H2O and
Cu3[Zr2F14]18H2O. Stoichiometry does not, in all cases, define coordination type. Consider the
following [MF6]2- complexes which ostensibly are 6-coordinate but indeed could be 6-, 7-, or 8coordinate, depending on the counter anion. In Rb2MF6, M is octahedrally coordinated whereas in
(NH4)2MF6 and K2MF6, polymerisation occurs to give 7- and 8-coordinated species (M = ZrIV or
Hf I V ).
The alkoxides
The alkoxides of the three metals, M(OR)4, are well characterised but it is those of titanium which are
of particular importance. The coordination number of 4 is very low for Zr4+ and Hf 4+ and therefore
forms intermolecular bridge of the type
R
O
/ \
M M
giving polymers. Polymerisation could be prevented by steric hindrance where the alkyl group is
bulky. In such cases, stable volatile monomers form.
+ 4EtOH base
Zr(OEt)4
ZrCl4
+ 4HCl
33
3.
3.1
PHYSICAL PROPERTIES
Electronic structure
V
Nb
Ta
Atomic number
23
41
73
Electron Config.
[Ar]3d34s2
[Kr]4d35s2
[Xe]4f145d36s2
Metal radius/pm
134
146
146
54
64
64
IV
58
68
68
III
64
72
72
II
79
1915
2468
Melting point/C
3.1.2
2980
abundance and 5th most abundant transition metal (after Fe, Ti, Mn, and Zr)
3.1.3
Nb
20 ppm
Ta
1.7 ppm
In view of their chemical similarities, niobium and tantalum invariably occur together, and their chief
mineral (Fe,Mn)M2O6, (M = Nb,Ta) is known as columbite or tantalite, depending on which metal is
of higher concetration. Pyrochlorite, CaNaNb2O6F, is fairly free of tantalum. They are prepared on a
small scale and the processes involved are varied and complicated. The ore is fused with alkali
followed by aqueous acid washing or digestion with acid and then separated. In dilute HF tantalum
tends to form the sparingly soluble K2TaF7 whereas niobium forms the soluble K3NbOF52H2O and
therefore can be separated. Process that is more recent involves the employment of solvent extraction
techniques. This uses a counter current liquid-liquid extraction of the metals into isobutylmethyl
ketone from HF.
3.1.4
USES:
Nb is used in the production of stainless steel for use at high temperatures.
Nb/Zr wires are used in superconductivity magnets.
Ta is extremely corrosive-resistant at normal temperatures and therefore used as a liner in the
construction of chemical plants.
Ta is inert to body fluids. It is therefore an ideal material for surgical use in bone repair and
internal surturing.
Ta is also used widely in the electronics industry in the manufacture of capacitors where the
oxide film is an efficient insulator, and as a filament or filament support.
34
3.1.5
CHEMICAL REACTIVITY
They are generally resistant to corrosion, due to the formation of surface films of oxide (most
effective in Ta). Ta is attached by oleum, HF (more particularly a HF/HNO3 mixture) when heated
and fused alkalis. V and Nb are, in addition to these reagents, attacked by other hot conc. mineral
acids but resistant to fused alkali.
As expected, Nb and Ta are chemically similar (except for small differences). The stability of lower
oxidation states decreases down the group. Although each element shows the formal oxidation states
from +5 to -1, the most stable one in the case of vanadium, under normal conditions, is +4. The +3
and +2 oxidation states, which are strongly reducing, have well-characterised cationic aqueous
chemistries. Most of the chemistries of Nb and Ta are confined to the group oxidation state of +5. Nb
and Ta, unlike, V, do not form positive ions. Their compounds in the +5 state are essentially covalent,
volatile, and readily hydrolysed.
At +3 state Nb and Ta do not exhibit the cationic chemistry observed in vanadium in the +3 and +2
oxidation states. Instead, they form a series of cluster compounds consisting of octahedral M 6X12
units. This is possible because of formation of strong metal-metal bonding in Nb and Ta.
3.1.6
The oxides
+5 State: M2O5
The oxides become increasingly more basic as the group is descended. V2O5 is amphoteric but mainly
acidic. It therefore dissolves readily in NaOH forming a wide range of vanadates and also dissolves
sparingly in conc. H2SO4 forming VO2+ ions.
Nb2O5 and Ta2O5 are un-reactive but are amphoteric, with very weak acidic properties. The niobates
and tantalates formed when fused with NaOH are decomposed by weak acids or CO2. In the
pentoxides the metal atoms have a d0 configuration and are expected to be colourless. Nb2O5 and
Ta2O5 are colourless but V2O5 is orange/red due to charge-transfer transitions.
Lower oxidation states
MO2 (M = V, Nb, Ta) are known. Only V2O3 is known at +3 state and though MO are known for M =
V and Nb the existence of TaO is not yet confirmed.
Halides and oxohalides
Halides
The following can be extracted from the table below:
Vanadium(V) is formed only as the fluoride and vanadium(IV) does not form the iodide.
However, all the halides of vanadium(III) and (II) are known.
Niobium and tantalum, on the other hand, form all the halides in the higher oxidation state, and
are in fact unique in forming pentaiodides but, even in the +4 state, Ta fails to form a fluoride
and neither metal produces a trifluoride. The dihalides of Nb and Ta are unknown. However,
clusters of [M6X12]n+ units are common (p. 13).
35
Oxidation
State
+5
Fluorides
Chlorides
VF5(Colourless)
+4
+3
Iodides
-
NbF5(white)
NbCl5(yellow)
TaF5(white)
TaCl5(white)
VF4
VCl4
VBr4
NbF4
NbCl4
NbBr4
NbI4
TaCl4
TaBr4
TaI4
VCl3
VBr3
VI3
VI3
VF3
+2
Bromides
NbF3(?)
NbCl3
NbBr3
TaF3(?)
TaCl3
TaBr3
VF2
VCl2
VBr2
VI2
The pentafluorides are white, pentachlorides - yellow, bromides - orange and the iodides - brown.
The increasing energy of the charge-transfer bands responsible for the colours is a reflection of the
increasing polarizability of the anion from F- to I-. For each anion it is the least readily reduced Ta
which produces the palest colour. Another feature, which would be evident later, is the characteristic
feature of the chemistry of the lower halides of Nb, Ta; Mo, W; Re, which display ability to form
metal clusters.
Preparation of the halides
Pentahalides
When heated with all the halogens, Nb and Ta, give the pentahalides, MX5, but for V the oxidation
state formed depends on the particular halogen: VF5, VCl4, VBr3, and VI2.
Other methods include:
Treatment of tantalum metal with
(a)
Cl2/Ar at 300 or
(b)
HCl gas at 400;
Treatment of Ta2O5 with
(a)
carbon and Cl2 at 500 or
(b)
CCl4 at 300
Treatment of hydrous Ta2O5 with boiling SOCl2 (best);
Treatment of Ta2S2 with Cl2 at 300.
Write balanced equations for all the above reactions.
36
The pentahalides are all relatively volatile, hydrolysable solids (indicative of the covalency at such a
high oxidation state) in which the metals attain octahedral coordination via halide bridges.
VF5 is an infinite chain polymer; NbF5 and TaF5 are tetramers and MCl5 and MBr5 are dimers.
All the pentahalides are potential Lewis acids but their ability to form adducts (LMX5) diminishes and
the iodides rarely do so.
Tetrahalides
The tetrahalides of V can be prepared directly from the elements. VF4 tends to dispropotionate into
VF5 + VF4; VCl4 and VBr4 tend to dissociate into VX3 + X2. The Nb and Ta tetrahalides (except
TaF4, which is unknown, and NbI4 which is generally prepared by thermal decomposition of NbI5) are
generally prepared by reduction of the pentahalide and are all readily hydrolysed. NbF4 consists of
infinite sheets of NbF6 octahedral. The low magnetic moment suggests extensive metal-metal
interactions, presumably via F- ions. The chlorides, bromides, and iodides are brown to black solids
with a chain structure in which metal-metal interaction is facilitated; thus leading to their
diamagnetism (cf NbF4 is paramagnetic).
The lower halides
These halides are rather complicated. There are three main types:
(a)
(b)
(c)
(b) and (c), e.g. Nb3Cl8, tend to be non-stoichiometric. NbF3, TaF3 and NbI3 are stoichiometric
trihalides. The existence of TaI3 is uncertain. The bromides and iodides form compounds based on
M3X8 where evidently there is a deficiency of metal.
At +2 oxidation state the halides of vanadium are clearly different from the halides of niobium and
tantalum. The vanadium dihalides, like the trihalides, are strong reducing agents, hygroscopic and
dissolve in water to give [V(H2O)6]2+ ions. By contrast Nb and Ta dihalides are compounds based on
[M6X12]n- units, consisting of octahedral clusters of metal atoms. Two series can be identifoed:
[M6X12]X4/2 = M6X14 (i.e. MX2.3) - these compounds are diamagnetic as a result of metal-metal
bonding.
[M6X12]X 6 2 = M6X15 (i.e. MX2.5) these have magnetic moments corresponding to 1 unpaired
electron per hexamer and so indicates the same metal-metal bonding within the cluster.
If the Nb6Cl14 is dissolved in water and alcohol, 2 moles of AgCl is precipitated by the addition of
AgNO3. This indicates the presence of [Nb6Cl12]2+ ions.
Write an equation for the reaction described here.
37
Oxohalides
Oxidatio
n State
Fluorides
Chlorides
Bromides
Iodides
+5
VOF3
VO2F
VOCl3
VOBr3
NbO2F
NbOCl5 NbO2Cl
NbOBr3
NbOI3
TaO2F
TaOCl3 TaO2Cl
TaOBr3
VOCl2
VOBr2
TaOF3
+4
VOF2
VO2Cl
NbOCl2
NbO2I
TaO2I
NbOI2
TaOCl2
+3
VOCl
VOBr
They are limited to the oxidation state +4 and +5. The +4 state are relatively stable whereas those at
+5 state are hygroscopic and hydrolyse vigorously in water. The Nb(V) and Ta(V) oxohalides are
rather volatile but less than the pentahalides.
MX5 (or MOX3) behave as Lewis acids and therefore can react with Lewis bases to form adducts of
the type discussed for the Ti group. The halogens can also be replaced by alkoxide (OR),
dialkylamide (NR2) and alkyl (CR3) groups.
2NH
e.g. 2TaCl5 + 10ROH Et
Ta2(OR)10 + 10HCl
2TaCl5 + 3ZnMe2
2TaCl2(CH3)3 + 3ZnCl2
NbCl5 + 5LiNR2
Nb(NR2)5 + 5LiCl
MCl5 + 3Ph3PO
MOCl3(Ph3PO)2 + Ph3PCl2
38
4.1
PHYSICAL PROPERTIES
4.1.1
Electronic structure
Cr
Mo
Atomic number
24
42
74
Electron Config.
[Ar]3d54s1
[Kr]4d55s1
Metal radius/pm
128
139
139
VI
44
59
60
49
61
62
IV
55
65
66
III
61.5
69
[Xe]4f145d46s2
II
Melting point/C
4.1.2
73(ls), 80(hs)
1900
2610
(3380)
Ores
Cr
Chromite, FeCr2O4 is the most important ore. Crocoite, PbCrO4, and chromo ochre, Cr2O3 are
less plentiful. Gemstones and ruby owe their colours to traces of chromium. South Africa has
96% of World reserve of Cr.
Mo
4.1.3
MoS2 (as primary and by-product of copper) is separated by floatation and then roasted to MoO3
85% of MoO3 is used in the manufacture of stainless steel and high-speed tools. MoO3 can also be
converted to ferromolybdenum (stainless steel) by the aluminothermic process. It can also be purified
by dissolutions in aqueous ammonia and crystallised as ammonium molybdate (sometimes as the
dimolybdate, (NH4)2[Mo2O7] or paramolybdate, (NH4)6[Mo7O24]4H2O, depending on condition),
which is the starting material for the manufacture of molybdenum chemicals. Pure Mo (an important
catalyst in a variety of petrochemical processes and an important electrode material) can be obtained
by hydrogen reduction of ammonium molybdate.
39
The isolation of tungsten is effected by the formation of tungstic acid (hydrous WO 3), but the
chemical route chosen depends on the ore being used. After pulverization and concentration of the
ore:
(a)
Wolframite is converted to soluble alkali tungstate either by fusing with NaOH and leaching
the cooled product with water, or by protracted boiling with aqueous alkali. Acidification with
HCl then precipitates the tungstic acid.
(b)
Scheelite is converted to insoluble tungstic acid by direct treatment with HCl and separated
from the soluble salts of other metals.
Tungstic acid is then roasted to WO3, which is reduced to the metal by heating with hydrogen at 850.
50% of the tungsten produced is used as the carbide, WC, which is extremely hard and wear-resistant
and so ideal as a tool-tip. Many heat-resistant alloys are also produced. The most important use of
the pure metal is as a filament in electric light bulbs (first used in 1908). Molybdenum disulphide is
used as a graphite-like lubricant, since it has a layer structure. Mo is important biologically in the
nitrogen-fixing enzyme nitrogenase and exists in other proteins e.g. xanthine oxidase.
4.1.4
Properties
Mo and W are refractive. W has the highest melting point of all metals, indeed of all elements except
carbon. For this reason, metallic Mo and W are fabricated by the techniques of powder metallurgy.
4.1.5
Chemical reactivity
At ambient temperatures, the elements resist atmospheric attack, which is why Cr is so widely used to
protect other more reactive metals (chrome plating). They are more susceptible to attack at high
temperatures when they react with many non-metals to form interstitial and non-stoichiometric
products. Cr reacts more rapidly with acids than Mo or W, though reactivity depends on purity and it
can easily be rendered passive. Thus it dissolves in dilHCl but resists dilH2SO4, if very pure. HNO3
(dil. or conc.) and aqua regia render Cr passive. The metals react with alkali metals in the presence of
oxidising agents (e.g. KNO3 or KClO3) to give MO42-. The two heavier metals are dissolved by mixed
acids, HF/HNO3, and by fused sodium peroxide.
Mo and W are closely similar to each other and are markedly different from Cr. This is reflected in
the relative stabilities of the oxidation states, all of which are known from +6 to -2. While Cr(VI)
tends to form polyoxoanions they are less diverse as polymolybdates and polytungstates. Although
Cr(V) and Cr(VI) are unstable, Mo(VI) and W(VI) as well as Mo(V) and W(V) provide a significant
aqueous chemistry at these oxidation states.
For Cr, the +3 state is the most stable oxidation state and enjoys extensive coordination chemistry
whereas Cr2+ is strongly reducing. The +VI state is the most stable and important for Mo and W. Both
Cr3+ and Cr2+ have extensive cationic chemistry while Mo(III) and W(III) are strongly reducing and
Mo(II) and W(II) are stabilised only by metal-metal bonding, e.g. the cluster compounds based on [M6
X8]4+ unit. Strong M-M multiple bonds occur with each of the divalent elements (less extensive with
W than with the other two). The +3 state for Mo and W is strongly reducing. These observations fit
the usual trend that on descending a group the higher oxidation states become more stable and the
lower oxidation states become less stable. The zero oxidation state arises in metal carbonyls such as
Cr(CO)6 , Mo(CO)6 and W(CO)6 , where the bonding electrons are donated by the CO group, and
d-p backbonding occurs from the filled metal orbitals.
4.2
4.2.1
The oxides
40
The principal oxides are the trioxides, MO3. CrO3 is strongly acidic and rather covalent with m.p. of
197 (Cr(VI) is small). It is commonly called chromic acid and is prepared by adding conc. H 2SO4
to a saturated aqueous solution of a dichromate.
Na2Cr2O7 + H2SO4 2CrO3 + Na2SO4 + H2O
CrO2 is strongly oxidising and loses oxygen in a succession of lower oxides until Cr2O3 is formed on
heating above 220-250. It is toxic and corrosive. MoO3 and WO3 are made by heating hydrous
trioxides (which are themselves obtained by acidification of aqueous molybdates or tungstates) or by
heating the metals in oxygen. Although MoO3 and WO3 are acidic too and dissolve in aqueous alkali
to give salts of the MO42- ions, they are insoluble in water and have no appreciable oxidising
properties, being the final product of the combustion of the metals. Their melting points (MoO3, 795;
WO3, 1473) are much higher than for CrO3 and their crystal structures are different. If either MoO3
or WO3 is heated in vacuo or is heated with the powdered metal, reduction occurs until eventually
MO2 is formed. An array of intermediate non-stoichiometric oxide phases between MO3 and MO2 are
known (e.g. Mo4O11, Mo17O47, Mo8O23 , W18O49 and W20O58).
Molybdenum forms a violet pentoxide, Mo2O5, on heating the trioxide with the metal. Both metals,
however, form the dioxides on careful reduction of the trioxide with hydrogen. MoO2 and WO2 are
both diamagnetic presumably as a result of a close M-M distance.
Only Cr2O3 is known at +3 state. It is the most stable oxide of Cr and is the final combustion of the
metal. It is conveniently made by thermal decomposition of ammonium dichromate.
(NH4)2Cr2O7
Cr2O3 + N2 + 4H2O
It is used as a pigment. When produced by dry methods it is unreactive but if precipitated as the
hydrous oxide (or hydroxide) from aqueous Cr(III) solutions it is amphoteric. It dissolves in
aqueous acids to give an extensive cationic chemistry based on [Cr(H2O]6]3+ ion, and in alkalis to
produce complicated, extensively hydrolysed chromate(III) species.
CrO2 has metallic conductivity and its ferromagnetic properties lead to its use in the manufacture of
magnetic recording tapes, which are claimed to give better resolution and high frequency response
than those made from iron oxide.
4.2.2
Isopolymetallates
The oxides MO3 (M = Cr, Mo, W) are strongly acidic, and dissolve in aqueous NaOH forming
discrete tetrahedral chromate, CrO42- ; molybdate, MoO42- ; and tungstate, WO42-.
MO3 + 2NaOH
2Na+(aq) + MO42-(aq) + H2O
Chromates, molybdates and tungstates exist both in solution and as solids. Chromates are strong
oxidising agents
41
H+ + CrO42-
HCrO4-
K = 105.9
H.CrO4- + H+
H2CrO4-
K = 10-0.26
2 H.CrO4-
Cr2O72- + H2O
K = 102.2
H+ + Cr2O72-
HCr2O7-
K = 10-0.85
HCr2O72- + H+
H2CrO4
K = small
These equilibria are pH-controlled and polymerisation beyond the dichromate ion is limited to the
formation of tri and tetra-dichromates (Cr3O102- and Cr4O132-), which can be crystallised as alkalimetal salts from very strongly acidic solutions. The corner sharing of CrO4 tetrahedra, giving Cr-OCr angles of about 120o, forms the dichromate and the tri- and tetra-chromates. The simplicity of this
anionic polymerisation of chromium is probably due to the small size of CrVI. This limits it to
tetrahedral rather than octahedral coordination with oxygen, whilst simultaneously favouring Cr-O
double bonds and so inhibiting the sharing of oxygens.
When molybdate and tungstate solutions are acidified they yield the most complicated of all the
polyanion systems. Dissolutions of MoO3 and WO3 in aqueous alkali give solutions containing
tetrahedral MO42- ions from which simple molybdates and tungstates (e.g. Na2MO4) can be
crystallised. When the solutions are made strongly acidic (less than pH 1) yellow molybdic acid,
MoO32H2O or white tungstic acid, WO32H2O are obtained. At intermediate pHs, however,
polymeric anions, containing MO6 octahedral moiety are formed and their salts can be crystallised. V,
Nb, Ta and U also form polyacids, but to a lesser extent. The MoO6 or WO6 octahedra are joined
together in a variety of ways by sharing corners or edges, but not faces. Important differences
distinguish the Mo and W systems. In aqueous solution, equilibration of the molybdenum species is
complete within a matter of minutes whereas for tungsten this may take several weeks.
The polyacids of Mo and W are divided into two main types:
1.
Isopolyacids in which the anions that condense together are all of the same
type; for example all MoO6 groups or all WO6 groups.
2.
Heteropolyacids in which two or more different types of anion condense together with, for
example, molybdate or tungstate groups with phosphate, silicate, borate groups.
The first step in polyacid formation as the pH is lowered is to increase the coordination number of Mo
or W from 4 to 6 by adding water molecules.
The first major polyanions formed when the pH of an aqueous molybdate solution is reduced below
about 6 is the heptamolybdate, [Mo7O24]6-. Anions with 8 and 26 Mo atoms are also formed before
the increasing acidity suffices to precipitate the hydrous oxide. This can be represented as:
42
[MoO4]4- pH6
[Mo7O24]6- pH1.5-2.9
[Mo8O26]4- pH<1
MoO32H2O
normal molybdate
paramolybdate
octamolybdate
hydrated oxide
(Moldybdic acid)
The present understanding of the tungstates is summarised below:
slow
[WO4]2[HW6O21]5[W12O41]10- or [W12O36(OH)10]10normal
boil OH- paratunstate A days/weeks
paratungstate B
tungstate
pH = 3.3
[H3W6O21]3- or [HW6O203-]n
[H2W12O40]6weeks / months
4-metatungstate
(pseudo-metatungstate)
pH~1
WO32H2O
hydrated oxide (tungstic acic)
H+
metatungstate
Heteropolymetallates
43
4.2.4. Halides
Oxidation
state
Fluorides
Chlorides
Bromides
CrF6
MoF6
WF6
WCl6
WBr6
CrF5
MoF5
WF5
MoCl5
WCl5
WBr5
+4
CrF4
MoF4
WF4
CrCl4
MoCl4
WCl4
CrBr4?
MoBr4
WBr4
CrI4
MoI4?
WI4?
+3
CrF3
MoF3
CrCl3
MoCl3
WCl3
CrBr3
MoBr3
WBr3
CrI3
MoI3
WI3
+2
CrF2
CrCl2
MoCl2
WCl2
CrBr2
MoBr2
WBr2
CrI2
MoI2
WI2
+6
+5
Iodides
+VI halides
All the hexahalides can be prepared by reacting halogens directly with the metal and all are readily
hydrolysed. CrF6 is very unstable and decomposes into CrF5 and F2. MoF6 and WF6 are very stable,
low melting and volatile. CrF6 is also strongly oxidising. Only W is known with some certainty to
produce other hexahalides, WBr6 being susceptible to reduction.
+V halides
Only Cr forms a fluoride, a bright red, volatile solid, which is prepared from the elements using less
severe conditions than for CrF6. It is strongly oxidising.
MoF5 and WF5 can be prepared by reduction of the hexahalides with the metal but the latter
disproportionates to WF6 and WF4 if heated above 80. MoCl5 and WCl5 are known compounds.
MoCl5 is obtained from the corresponding elements under carefully controlled conditions. WBr5 is
prepared in a similar fashion. The pentahalides of Mo and W, when monomeric, are coordinatively
unsaturated and consequently tend to polymerise readily. Thus, MoF5 has a tetrameric structure of
four octahedra joined into a ring type structure, for example NbF5 and TaF5. MoCl5 is dimeric,
Mo2Cl10, in the solid state in the same way as NbCl5 and TaCl5 but monomeric and trigonal
44
bipyramidal in the vapour phase and in benzene solutions. The Mo-Mo is long and Mo2Cl10 has a
temperature-independent magnetic moment of 1.67 BM(i.e. one unpaired electron) which suggests
there is no direct metal-metal interaction. WCl5 is also a dimer.
+IV halides
The three tetraiodides together with CrBr4 and CrI4 have either uncertain existence or occur only at
high temperatures in the gaseous phase. The fluorides are the most stable.
CrF4 is formed by heating the elements at 350 and is unreactive. MoF4 is an involatile solid and WF4
begins to decompose only when heated to above 800. MoCl4 exists in two polymeric forms, one like
NbCl4 and TaCl4, having metal-metal bonds, and the other without metal-metal bonds. The second
displays normal magnetic moment expected for two unpaired electrons (eff = 2.42 BM).
+III halides
The trihalides show major differences between the three metals. All the CrX3 are known, and dissolve
in water to give [Cr(H2O6]3+ ions. They can be prepared by reacting the halogen and the metal,
though CrF3 is obtained in a higher yield from HF and CrCl3 at 500. Stable hydrated CrX3 can also
be obtained from aqueous solutions, e.g. CrCl36H2O.
All the trihalides of Mo and W are known, except WF3 (there are no simple +3 ions of Mo and W).
Mo trihalides are obtained by reducing a higher halide with the metal (except the triiodide, which,
being the highest stable iodide is best prepared directly from the elements). Two solid forms of
MoCl3 are known. In both, there is metal-metal interaction. The halides react with halide ions in
solution to form octahedral complexes,
MoCl3 + 3Cl-
[MoCl6]3Evidence of metal-metal interaction in MoCl3 is reflected in the low and temperature-dependent
magnetic moment.
Electrolytic reduction of a solution of MoO3 in aqueous HCl changes colour to green, then brown and
finally to red, when complexes of the octahedral [MoCl6]3-, Mo(Cl5(H2O)]2- and [Mo2Cl9]3- can be
isolated using suitable cations. In contrast, W III compounds are unstable.
The tungsten trihalides are cluster compounds. WCl3 exists as W6Cl18 and forms a cluster compound
[W6Cl12]6+ structurally similar to [Nb6Cl12]2+. WBr3 is W6Br18 and a cluster compound whose
structure contains [W6Br8]6+ and has the same structure as [Mo6Br8]4+.
The trichloride and tribromide are obtained by halogenising the dihalides. The tendency to form
cluster compounds is in the order CrIII<MoIII<WIII.
+II halides
Anhydrous dihalides of Cr can be made either by reductions of the trihalides with hydrogen at 500 or
from the metal and HF, HCl, HBr or I2 at 600. They are all readily oxidised by air to Cr3+ state. The
most important is CrCl2 which dissolves in water in an inert environment to give a sky blue complex,
[Cr(H2O)6]2+. The strongly reducing properties of Cr2+ halides contrast with redox stability of MoII
halides. Surprisingly though WII halides, in deviation of the expected trend, is a strong reducing agent
being oxidised to the trihalides. All the six dihalides of Mo and W (Mo and W do not form
difluorides) exist as M6X12 and are isomorphous with a structure based on [M6X8]4+ clusters. The Mo
clusters differ in that they do not undergo reversible oxidation, but W6Cl12 can be oxidised by Cl2 at
high temperatures.
45
There is extensive M-M bonding, and eight face bridging halogen atoms occupy the eight triangular
faces of the octahedron. The M6X84+ units can accept six coordinate bonds to the metal atoms at the
corners of the octahedron from the remaining four X- ions and two H2O molecules, or from any other
electron pair donor. Addition of six Cl- gives the [Mo6Cl14]2- cluster. Unlike Cr2+, these lowoxidation state clusters are not readily oxidised. However, [Mo6Cl8]4+ is oxidised to [Mo6Cl12]3+ and
[W6Cl8]4+ is oxidised to the [W6Cl12]6+ cluster.
4.3
The existence of compounds with triple and quadruple M-M bonds was recognised in about 1964 but
the chemistry was already extensively developed. Mo is the most prolific of multiple M-M bonds.
The quadruple bonds are more common than the triple bonds. Mo forms several hundreds such
compounds, many of which are stable in air at room temperature, whereas W has so far yielded only a
few. The reasons are not clear. A convenient entry into the Mo24+ compounds is by the reaction of
Mo(CO)6 with acetic acid in diglyme, which gives the compound Mo2(O2CCH3)4. One of the few
stable compounds exhibiting a W-W quadruple bond is
H3C
It has Mo2 and Cr2 analogues. Managanese group (manganese, technetium and rhenium), Iron group
(iron, ruthenium and osmium), Cobalt group (cobalt, rhodium and iridium) and Nickel group (nickel,
palladium and platinum) could also be covered in this module. The three groups covered have
sufficiently illustrated the general trends discussed in the first lecture.
46
SECTION C
COORDINATION CHEMISTRY
47
COORDINATION CHEMISTRY
5.1
Preliminary Comments
Historical highlights
Earliest record of coordination compound was Prussian blue, KCN.Fe(CN)3.Fe(CN)2, which was
obtained by the artist maker, Diesbach in the 18th century. The date usually cited is the discovery of
hexaamminecobalt(III) chloride, accidentally, by Tassaert in 1798, which marked the beginning of
coordination chemistry. It took about 100 years later before any explanation was forthcoming on how
CoCl3.6NH3 was possible. Following this discovery subsequent work was expectedly on complexes
of ammonia.
The naming of metal complexes has gone through a number of changes, viz:
Naming after the discoverers, e.g. Reineckes salt, Cr(SCN)3.NH4SCN.2NH3, now formulated
as NH4[Cr(SCN)4(NH3)2]; Zeises salt, PtCl2.KCl.C2H4 or K[PtCl3(C2H4)]
Naming according to colour, e.g. yellow CoCl3.6NH3 called luteocobaltic chloride and purple
CoCl3.5NH3 called purpurecobaltic chloride.
IUPAC nomenclature, which is the acceptable modern method of naming and will be
discussed in detail in this course.
Techniques employed in characterizing coordination compounds by the pioneer workers
Simple chemical reactions, e.g. [Co(NH3)5Br]SO4 (A) or [Co(NH3)5SO4]Br (B) involves
reacting solutions of each compound with either BaCl2/Ba(NO3)2 solution ((A gives a white
precipitate whereas B does not) or AgNO3 solution (A does not give any precipitate but B
gives a light yellow precipitate).
Conductivity experiments to determine the number of ions present in solution, e.g.
CoCl3.6NH3 (C) and CoCl3.5NH3 (D) above in which a known mass of each is dissolved in
standard flasks and their conductivities determined. (C) gives a 1:3 electrolyte (i.e. one cation
and three anions) whereas (D) gives a 1:2 electrolyte (one cation and two anions).
Gravimetric analysis, e.g. (C) and (D) could be distinguished gravimetrically by taking a
known mass of each, dissolve in water, and add excess AgNO3 solution to each. The white
precipitate formed in each case can be filtered in a dry pre-weighed crucible, washed free of
soluble impurities and dried to constant mass in an oven (at a prescribed temperature). The
crucible with the content is weighed and the mass of AgCl precipitated in each case is
calculated. From the mass of the precipitate the mass of Cl- in each case is calculated. (C)
would give 3 moles of Cl- (3 moles of AgCl) and (D) gives 2 moles of Cl- (2 moles of AgCl) if
1 mol dm-3 solution of each is used.
Write balanced equations for the reactions of compounds C and D with AgNO3
identify the precipitates
described and
Werner Theory
Werner proposed two valences for most elements:
Primary valence (now known as oxidation state) and secondary valence (now known as
coordination number). Every element tends to satisfy both its primary and secondary valences.
The secondary valence is directed towards fixed positions in space (i.e. secondary valence
determines the stereochemistry of compounds)
These constitute Werners coordination theory proposed in 1893 at the age of 26 and for which he
won a Nobel Prize in 1913. His theory has remained a guiding principle in Inorganic Chemistry and
in the concept of valence.
For example, CoCl3.6NH3 has a primary valency of 3 and a secondary valency of 6.
48
5.2
Preparation of compounds is the trade mark of every chemist. Research in chemical industries is
largely oriented toward the synthesis of new and useful materials. The chemist is interested in
preparing new compounds because it is an invaluable way of expanding our knowledge of chemistry.
There are many routes, but related experimental methods to preparing metal complexes. The method
chosen depends upon the metal, the oxidation state of the metal, the ligand and the electron
configuration of the ion. Not all methods can therefore be employed to the synthesis of a particular
compound. Having found a suitable method for making the compound in good yield one needs to find
a suitable way to isolate the product from its reaction mixture.
Some of the commonly used techniques to obtain products from reaction mixtures are:
Evaporation of the solvent to concentrate (could be under reduced pressure usin a rotary
evaporator) and the cooling in an ice-bath (or a refrigerator). Adding a seed crystal of the
desired compound (if available, and often it is not available) or scratching the inside of the
beaker below the liquid surface helps to induce crystallization.
A slow addition of a solvent that is miscible (but less polar) with the solvent of the reaction
mixture but which does not dissolve the desired product followed by cooling, (seeding), and
scratching.
For a cationic complex an appropriate anion with which it forms an insoluble salt can be
added. A suitable cation may be added to the reaction mixture containing an anionic complex.
E.g. to precipitate [Ni(CN)5]3- from a solution add a large trivalent cation like [Cr(en)3]3+ to
give [Cr(en)3][Ni(CN)5].
Chromatography can be used to separate and purify complexes.
Other techniques are distillation (could be under reduced pressure if the compound
decomposes before its boiling point) and sublimation (for volatile complexes), and Soxhlet
extraction (of either the complex, if soluble in extractor solvent or of the impurity if the
complex is insoluble).
5.2.1
There are two important variables that occur in reactions involving transition metals:
Coordination number
Oxidation state.
Either may increase, decrease, or remain unchanged in a reaction. It is, in practice, not possible to
predict either of these variables in a reaction. This is because ligands behave in peculiar way
depending on a number of constraints. E.g. a tetradentate ligand may behave as a bidentate ligand. It
is also possible for a ligand, which should be anionic, to coordinate neutral or as a radical. Whether a
reaction results in a change of oxidation state of the central metal or not would depend on the mode of
coordination of the resulting complex.
In general the following classifications hold:
Addition reaction: Coordination number of an electron acceptor (the metal/metal ion)
increases.
Substitution reaction: Coordination number is unchanged.
Dissociation reaction: Coordination number decreases.
Oxidation reduction reaction: There is a change in oxidation state.
Coordination compounds are also classified according to the speed at which they undergo substitution
reaction:
Complexes that undergo substitution reaction at room temperature spontaneously are said to be
kinetically labile.
Those where substitution takes hours/days are said to be kinetically inert.
49
5.3
5.3.1
Labile complexes
Complexes with central metal atom having d electrons in the eg orbitals, e.g. [Ga(C2O4)3]3-,
d10; [Co(NH3)6]2+, d7+; [Cu(H2O)6]2+, d9; [Ni(H2O)6]2+, d8 and [Fe(H2O)6]3+, d5.
Complexes containing less than 3 electrons in the d orbitals , e.g. [Ti(H2O)6]3+, d1;
V(phen)3]3+, d2 and [Ca(EDTA)]2+, d0+.
5.3.2
Inert complexes
Octahedral low-spin d4, d5 and d6 complexes, e.g. [Fe(CN)6]3-; [Co(NH3)6]3+ and [PtCl6]2-, d6.
Octahedral d3 complexes, e.g. [Cr(H2O)6]3+, d3.
Crystal field approach helps to see the picture clearly.
5.4
REACTIONS
50
Inert complexes are prepared from anhydrous complexes if non-aqueous medium is to be used.
Where only hydrated salts are available, salts have to be dehydrated first before use. If preparation is
to be done in aqueous medium then a labile complex of a lower oxidation state is oxidized or a salt at
a higher oxidation state is reduced.
Some ions are unstable to oxygen. Complexes of such ions are prepared in an inert atmosphere, e.g.
under N2 gas.
Examples
Substitution reaction in aqueous solution is the most common method for labile complexes. The
method involves a reaction between a metal salt in water and a coordinating agent.
Action of excess ammonia on aqueous solution of copper(II) salts:
[Cu(H2O)6]2+ + 4 NH3(l) [Cu(NH3)4]2+ + 6 H2O
or
[Cu(H2O)6]2+ + 4 NH3(aq) [Cu(H2O)2(NH3)4]2+ + 4 H2O
The instant replacement of water by ammonia at room temperature is shown by a change in colour.
Other species corresponding to stepwise substitution of the water by NH3 exist in solution, e.g.
[Cu(H2O)5(NH3)]2+, [Cu(H2O)4(NH3)2]2+, etc.
There are many labile complexes which may be studied readily in solution but which are very difficult
to obtain in the solid state.
Preparation of uncharged complexes
A neutral complex is usually precipitated from either aqueous solution or aqueous alcohol and, unless
highly polymeric, may be re-crystallized from organic solvents. For example,
[Cu(H2O)6]2+ + 2 Hacac
For this equilibrium to be displaced to the right (i.e. in favour of the formation of the complex) the
system is usually buffered to about pH 6. Sodium actate is commonly used.
Preparation of inert complexes
As mentioned earlier, substitution is usually slow and preparations can be done in three ways:
1.
If water is not being displaced and reaction is being done in water more drastic experimental
conditions are imposed.
For example the preparation of K3[Rh(C2O4)3] is done in boiling concentrated aqueous solutions of
K3[RhCl6] and K2C2O4 for 4 h and then evaporated until product crystallizes from the solution.
K3[RhCl6] + 3 K2C2O4
wine red
H2O, 4 h
100 oC
K3[Rh(C2O4)3] + 6 KCl
yellow
To prepare [Co(en)3]Cl3 from [CoCl(NH3)5]Cl2, the rection is carried out on a steam bath because the
reaction is slow at room temperature;
[CoCl(NH3)5]Cl2 + 3 en
[Co(en)3]Cl3 + 5 NH3
2.
If water is being displaced then the water has to be replaced first before he correct product can
be obtained.
For example, Cr(III) complexes cannot be made from aqueous solvents if water is undesirable in the
complexes (alternative routes are available).
51
For example potassium thiocyanate (m.p. 173o) can be used as a solvent at elevated temperatures
above 173o. Under this condition water is readily displaced from [Cr(H2O)6]3+.
3+
[Cr(H2O)6]
+ 6 NSC
180o
molten KCNS
[Cr(NSC)6]3-+ 6 H2O
In certain instances the salt is first dehydrated before the product can be obtained. Dehydration can be
effected by use of thionyl chloride or 2,2-dimethoxypropane. Preparation of anhydrous complexes are
best done from organic solvents and starting with, preferably, anhydrous salts, where they are
available.
Examples
1.
Consider the preparation of (NEt4)2[NiCl4] from [Ni(H2O)6]Cl2.
NiCl2 + 6 SO2 + 12 HCl
[Ni(H2O)6]Cl2 + 6 SOCl2
SOCl2
NiCl2 + 2 NEt4Cl
Reflux (NEt4)2[NiCl4]
Alternatively,
[Ni(H2O)6]Cl2 + 6 (MeO)2CMe2
NiCl2 + 2 NEt4Cl
2.
(NEt4)2[NiCl4]
[Cr(H2O)6]Cl3 + 6 (MeO)2CMe6
Cr(en)3]Cl3
CrCl3 + 3 en
5.4.5
Oxidation
Co(II) salts are usually used as starting materials for the preparation of Co(III) complexes;
CoCl2 + 2NH4Cl + 10 NH3 + H2O2
Charcoal
2 [Co(NH3)6]Cl3 + 2 H2O
Charcoal acts as a catalyst. In its absence the product is mostly [Co(NH3)5X] complexes, X = H2O or
Cl.
If it is only hydrated salts of an inert complex that is available it is best to dehydrate the salt first
before use.
Reduction
The preparation of K3[Cr(C2O4)3] from K2Cr2O7
Here the dichromate is reduced by an aqueous solution of oxalic acid and potassium oxalate:
K2Cr2O7 + 7 H2C2O4 + 2 K2C2O4
Note that in the instances where oxidation-reduction reactions are used the starting compounds are
labile. Cr(III) complexes can also be prepared from Cr(II). However, Cr(II) compounds are rather
unstable and can only be stored under inert atmosphere.
52
96.5o
CuSO4.4H2O
102o
CuSO4.3H2O
115o
CuSO4.H2O
220o
CuSO4
The blue hydrated copper(II) sulphate loses water stepwise until all the water of crystallization is lost
to give the off-white anhydrous salt. Controlled heating under vacuum is therefore a viable method
for making a number of complexes.
Examples
The conversion of [Cr(en)3]Cl3 to cis-[Cr(en)2Cl2]Cl is done by controlled heating:
[Cr(en)3]Cl3 cis-[Cr(en)3Cl2]Cl
5.5
53
1.
2.
3.
4.
Infrared spectroscopy (i.r.): Normally the infrared spectrum of the ligands and the complexes
are required for meaningful comparison. The differences between the spectra fall into four
categories:
Band positions may change
Relative band intensities may change. Usually new, often weak, bands may appear.
Single peaks in the free ligands may split into several, closely spaced, bands in the complex.
Some peaks in the ligand may disappear while new ones, particularly in the region due to
Metal Ligand bond (below 600 cm-1 may appear. Evidence for coordination and atoms in
coordination can be established from i.r. spectra. The mode of coordination of some anionic
ligands can also be detected.
Examples
CO32- can be monodentate or bidentate. Free CO32- absorbs at 890 cm-1; coordinated CO32absorbs at ~850 cm-1 (if monodentate) and at ~830 cm-1 (if bidentate).
SCN- can be S-bonded, where (C-S) is at ~700 cm-1 or N-bonded where (C-S) is at ~820 cm-1.
NO2- could be N-bonded [(N-O) is at ~1310 cm-1] or O-bonded [(N-O) is at ~1065 cm-1].
Stretching frequency in metal-oxygen double bond, as in V=O occurs at 960 50 cm-1.
Metal-ligand absorptions are generally weak and occur at 600 100 cm-1 region, which may
present instrumental problems. Usually any i.r. spectrometer that does not record to 200 cm -1 is of
limited use in coordination chemistry. This is the region to concentrate on for M-N, M-O, and MX frequencies.
Infrared spectra for coordination compounds are usually recorded preferably in the solid (KBr or
CsBr pellets). There are overlaps when run in Nujol and one cannot go below 600 cm-1 in Nujol.
Other techniques that can be used in the characterization of coordination compounds include:
UV-Visible spectroscopy
Photoluminescence
Magnetochemistry
Thermogravimetric analysis
Differential thermal analysis
Cyclic Voltammetry (for oxidation-reduction properties of complexes)
Mass spectrometry
Nuclear magnetic resonance spectrometry
Mssbauer Spectrometry
Optical rotatory dispersion and circular dichroism (for optically active complexes)
X-ray diffraction (which gives the ultimate structure of the compound unequivocally)
5.6
Nomenclature
The International Union of Pure and Applied Chemistry (IUPAC) system will be discussed.
5.6.1
Naming ligands
Ligands can be anionic or neutral. Both anionic and neutral ligands can
be monodentate or polydentate.
5.6.2 Anionic ligands
Anionic ligands end in -o
54
Name
Chloro
Bromo
Iodo
Hydroxo
Amido
Nitro
Nitrito
Cyano
Isocyano
Ligand
O2HO22CH3COOSCN-; M-SCN
NCS-; M-NCS
Name
Oxo
Hydrido
Peroxo
Acetato
S-thiocyanato
or thiocyanato
N-thiocyanato
or isothiocyanato
Name
Acetylacetonato or Pentane-2,4-dionato
Glyoximato
Oxalato
Dimethylglyoximato
Name
Aqua or aquo
Ammine
Carbonyl
Nitrosyl
Ligand
RNH2
py
(C6H5)3P
Name
Alkylamine
Pyridine
Triphenylphosphine
Bidentate
Lgand
en
Bipy
Name
Ethylenediamine
Bipyridine
Structure
NH2CH2CH2NH2
1,10-phen or phen
Phenathroline
5.6.4
Naming complexes
If it is a salt:
Name cation first and then the anions, like in all salts. There is a space between the cation and
the anion.
55
Within a complex:
Name negative ligands.
Name the neutral ligands.
Name the metal (with oxidation state, in Roman numeral, in brackets).
Where there is more than one type of ligand in a complex, name in alphabetical order or in order of
complexity where they start with the same alphabet.
For the number of ligand (of the same type) use di-, tri-, tetra-, penta- and hexa- for 2, 3, 4, 5, and 6
respectively.
If the ligands are multi-syllabic put the name of the ligand in parenthesis. The numerical prefixes are
changed to bis-, tris-, tetrakis-, pentakis, and hexakis- for 2, 3, 6.
In anionic complexes the name of the metal ends -ate. In some cases the Latin name is used; e.g.
iron becomes ferrate.
In cationic complexes the metal retains its English name.
Examples
[Cr(NH3)6](NO3)3
hexaamminechromium(III) nitrate
K2[PtCl6]
potassium hexachloroplatinate(IV)
K3[Fe(ox)3].3H2O
potassium trioxalatoferrate(III), trihydrate or 3-water
Na[Co(CO)4]
sodium tetracarbonylcobaltate(-I)
K4(Ni(CN)4]
potassium tetracyanonickelate(0)
[Co(en)2Cl2]Cldichlorobis(ethylenediamine)cobalt(III) chloride
[Co(NO2)3(NH3)3]
triamminetrinitrocobalt(III)
In a neutral complex, the ligands are named first adopting the rules above followed by the metal.
Example
[Ni(Hdmg)2]
bis(dimethylglyoximato)nickel(II)
Bridging complexes
Ligands that bridge two centres of coordination (polynuclear) are preceded by the Greek letter, ,
which is repeated before the name of each different kind of bridging group.
H
O
[(H2O)4Fe
Fe(H2O)4](SO4)2
O
H
m-dihyroxobis[tetraaquairon(III)] sulphate
or tetraaquairon(III)-m-dihydroxotetraaquairon(III) sulphate
H
N
[(en)2Co
Co(en)2]Cl4
O
H
bis(ethylenediamine)-m-imido-m-hydroxo-bis(ethylenediamine)cobalt(III) chloride
or m-hydroxo-m-imidobis[bis(ethylenediamine)cobalt(III)] chloride
56
H
N
[(NH3)4Co
Co(NH3)4] (NO3)4
N
O2
-amido--nitrobis[tetraamminecobalt(III)] nitrate
Point of attachment
Whenever necessary the point of attachment of a ligand is designated by placing the symbol (in
italics) of the element attached after the name of the group is separated by hyphen.
(NH3)3[Cr(NCS)6]
ammonium hexathiocyanato-N chromate(III) or
hexaisothiocynatochromate(III)
(NH3)2[Pt(SCN)6]
ammonium hexathiocyanato-S-platinate(IV)
Naming geometric isomers
Geometric isomers are generally named by the use of the terms cis to designate adjacent (90o apart)
positions and trans for the opposite (180o apart) positions. It is occasionally necessary to use a
number system to designate the position of each ligand. For square-planar complexes, groups 1-3 and
2-4 are in trans positions. Note that only two of the trans positions need be numbered in the name of
the second complex below. This is because in a square-planar complex the other two ligands must
then be in trans positions. Since positions 2 and 4 are equivalent these numbers need not be
mentioned.
1
4
3
Number system in square-planar complexes
-
Cl
NH3
Pt
NH3
NH3
Cl
NO2
trans-diamminechloronitroplatinum(II)
Pt
NO2
Br
1-ammine-3-bromochloronitroplatinum(II) ion
The number system for octahedral complexes has the trans positions numbered 1-6, 2-4, and 3-5.
57
1
2
5
+
NH3
NH3
NH3
M
4
6
NH3
Br
Rh
py
Br
Pt
Br
NO2
Cl
NH3
cis-tetraamminedibromorhodium(III) ion
I
1-ammine-2-bromo-4-chloro-6-iodonitro(pyridine)
platinum(IV)
or trans-ammineiodo-trans-bromochloronitro(pyridine)
platinum(IV)
5.7
Isomerism can be divided into two broad divisions: structural isomerism and stereoisomerism.
Structural isomerism: Ionization isomerism, hydration isomerism, coordination isomerism, linkage
isomerism, ligand isomerism, and polymerization isomerism.
Stereoisomerism: Geometric
isomerism, conformational isomerism, and optical isomerism.
5.7.1
Structural isomerism
[Cr(H2O)6]Cl3
Violet
[Cr(H2O)5Cl]Cl2.H2O
Blue green
[Cr(H2O)4Cl2]Cl.2H2O
Dark green
Other examples are [CoCl(en)2H2O]Cl2 and [CoCl2(en)2]Cl.H2O; [CrCl2(py)2(H2O)2]Cl and
[CrCl3(py)2H2O].H2O.
The isomers can be distinguished by quantitative precipitation of free chloride using silver nitrate.
Describe how you would carry out the quantitative precipitation of free chlorides in the isomers
above. Write appropriate equations and show how you would use your results to distinguish the
isomers.
Structural isomerism: coordination isomerism
Coordination isomerism occurs in salts in which both cation and anion are complex ions. Isomerism
arises from interchange of ligands between the two complex ions.
Examples:
[Co(NH3)6][Cr(ox)3] and [Cr(NH3)6][Co(ox)3]
[PtII(NH3)4][PtIVCl6] and [PtIV(NH3)4Cl2][PtII(NH3)4]
[Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]
[Co(NH3)6][Co(NO2)6] and [Co(NH3)4(NO2)2][Co(NH3)2(NO2)4]
Structural isomerism: linkage isomerism
Linkage isomerism occurs when one or more of the ligands can coordinate to the metal ion in more
than one way. Linkages with two or more possible sites of attachment to a metal are known as
ambidentate ligands. In principle they include NO2-, SCN-, CN-, S2O32-, CO, CONH2, CS(NH2)2, and
(CH3)2SO but only the first four have been shown to form linkage isomers.
Examples
[Co(NH3)5NO2]2+ and [Co(NH3)5ONO)]2+ are isomers . In the first one NO2- bonds to Co by N (a
nitro complex) whereas in the second it bonds by O (a nitrito complex). The complexes can be
distinguished by using IR spectroscopy. For the O-bonded ligand, characteristic absorption bands at
1065 and 1470 cm-1 are observed whereas corresponding bands for the N-bonded ligand are at 1310
and 1430 cm-1. The above complexes can be written as [Co(NH3)5(NO2-N)]2+ and [Co(NH3)5(NO2O)]2+ respectively.
[Co(NH3)5SCN]2+ has two isomers, [Co(NH3)5SCN-S]2+ and [Co(NH3)5SCN-N]2+, where SCN- bonds
via S and N respectively. Other examples can be found in complexes of CN- where the ligand can
bond by C (cyno complexes) or N (isocyano complexes).
Other examples: [dipyPd(SCN)2] and [dipyPd(NCS)2]; [Mn(CO)5SCN] and [Mn(CO)5NCS]. All
linkage isomers can be readily identified by IR spectroscopy.
e.g. M-N=C=S has a characteristic band at 780 860 cm-1 whereas in M-S-CN it occurs at 690 720
cm-1.
Structural isomerism: polymerization isomerism
Polymerization isomerism refers to complexes, which have the same empirical formulae but different
molecular masses.
Examples:
[PtCl2(NH3)2] and [Pt(NH3)4][PtCl4] and [Co(NH3)3(NO2)3] and [Co(NH3)6][Co(NO2)6]
Structural isomerism: Ligand isomerism
Ligand isomerism is due to isomerism in the organic compounds that constitute the ligands.
Since many ligands are organic compounds and the latter have a large number of possibilities for
isomerism, the resulting complexes can show isomerism from this source.
Examples of isomeric ligands are 1, 2-diaminopropane (pn) and 1,3-diaminopropane (tn) or o-, m- and
p-toluidine (CH3C6H4NH2). When these compounds are used as ligands the resulting complexes are
also isomeric.
e.g. [Co(pn)3 and [Co(tn)3 are isomers.
59
5.7.2
Stereoisomerism
Cl
NH3
Pt
NH3
NH3
Cl
NH3
NH3
NH3
The cis-isomer is
polar
NH3
Pt
NH3
Symmetric stretch
IR inactive
Cl
Cl
Cl
Pt
Cl
Asymmetric stretch
IR active
Cl
Pt
Pt
Cl
The trans-isomer is
non-polar
NH3
Cl
Cl
Cl
NH3
Asymmetric stretch
IR active
NH3
Pt
Cl
NH3
Symmetric stretch
IR active
60
A
D
Cl
NH3
NH3
Co
NH3
NH3
Co
NH3
NH3
NH3
NH3
Cl
cis-isomer
trans-isomer
MA3B3 type
Two types are possible: (1) here the ligands of one type forms an equilateral triangle on one of the
faces (the facial isomer, abbreviated as fac) and (2) the ligands span three positions such that two are
opposite, or trans, to each other (the meridional isomer, abbreviated as mer). The following
complexes can display the fac-mer isomerism: [Ru(H2O)3Cl3]; [Pt(NH3)3Br3]+; [Pt(NH3)3I3];
[Ir(H2O)3Cl3]; [Rh(CH3CN)3Cl3]; [Co(NH3)3(NO2)3]; and [M(CO)3PR3], (M = Cr, Mo, W).
Cl
H2O
OH2
Cl
H2O
Ru
H2O
Cl
Ru
Cl
Cl
H2O
Cl
H2O
mer-isomer
fac-isomer
61
P
Cl
Cl
Ni
Ni
Cl
P
P
Square-planar
P
Cl
P = PH2PCH2Ph
Tetrahedral
[] =
cxl
where = observed rotation, l = path length of solution in the polarimeter (in dm) and c =
concentration (in g cm-1). Light of a single frequency is used for specific rotation measurements and a
common choice is sodium D-line in the emission spectrum of atomic sodium; the specific rotation at
this wavelength is denoted as []D. The importance of chirality has been found in the dramatic
differences in the activities of different enantiomers of chiral drugs.
Read: E Thall (1996) Journal of Chemical Education, Vol. 73, p.481 When drug molecules look in
the mirror.
5.7.3
This method of naming defined in terms of an observable (the rotation) does not bear any direct
relationship with the absolute configuration of the molecule.
IUPAC recommended and system
Definitions and notation of chiral complexes
Enantiomers are a pair of stereoisomers that are non-superimposable mirror images.
Diastereomers are stereoisomers that are not an enantiomeric pairs.
(+) and (-)prefixes: the specific rotation of enantiomers is equal and opposite. Enantiomers are
distinguished by the sign of []D. Two enantiomers of a compound A with []D values of +12 and -12
are denoted as (+)-A and (-)-A.
d and l prefixes: sometimes (+) and (-) are denoted by dextro- and laevo- for right and left rotations
respectively.
The +/- or d/l notation, as mentioned above, has nothing to do with the absolute configuration of an
enantiomer (the arrangement of the substituents or ligands). The following prefixes are used for
describing absolute configuration.
R and S prefixes: this convention is used for labeling chiral carbon atoms (tetrahedral with four
different groups attached) and is based on the Cahn-Ingold-Prelog notation.
The four groups attached to the chiral carbon atom are prioritized according to the atomic number of
the attached atoms, highest priority being assigned to highest atomic number, and the molecule then
viewed down the C-X vector, where X has the lowest priority. The R- and S-labels for the
enantiomers refer to a clockwise (rectus) and anticlockwise (sinister) sequence of the prioritized
atoms, working from high to low. Example: CHClBrI, view down the C-H bond:
1
1
I
I
H
C
Cl
C
Br
Br
Cl
3
2
R
This notation is used for chiral organic ligands, and also for tetrahedral complexes.
and prefixes: The enantiomers of octahedral complexes containing three equivalent bidentate
ligands (tris-chelate complexes) are among those which are distinguished using (delta) and
(lambda) prefixes. The octahedron is viewed down a 3-fold axis, and the chelates then define either a
right- or a left-handed helix. The enantiomer with right-handedness is labeled , and that with lefthandedness is .
63
Depending on the metal ion and the number and nature of chelate rings enantiomers can be separated.
5.7.4 Rules for optical activity
An optically active compound must not have:
A centre of inversion
A plane of symmetry
An improper axis S
The mirror image must not be superimposable.
Examples of stereoisomers
[Co(en)2Cl2] can exist as cis- and trans-isomers. The cis isomer is potentially optically active because
its mirror image is not superimposable.
Cl
Cl
Co
N
N
Co
Cl
Cl
cis-[Co(en)2Cl2]
But the trans-isomer has a plane of symmetry and a centre of inversion. It is therefore not optically
active.
Cl
N
N
Co
Cl
trans-[Co(en)2Cl2]
The first compound to be resolved was cis-[Co(en)2(NH3)Cl]2+. It was resolved with (+)bromo-camphor sulphate. In the solid state, the enantiomorphs are stable. However, they often racemize in
solution and therefore may not be possible to isolate isomers even if you know they exist.
The best complexes to isolate and keep in solution are those where
M is inert (undergoes slow substitution); e.g. CoIII (d6) and CrIII (d3) complexes. For example
[Co(en)3]Cl3 is potentially active and boiling for hours will not convert one isomer to the other. On
the other hand [Zn(en)3]2+ racemizes very rapidly because Zn2+ is a d10 ion and is very labile.
Ligands are bidentate or polydentate. Such complexes are stabilized by chelate effect. Good
examples are found in EDTA complexes.
The first purely inorganic complex to be resolved into its optical isomers was [CoL3]6+, where L+
ligand = cis-[Co(NH3)4(OH)2]+ complex. L+ chelates through the two O-donor atoms.
64
6+
H
O
Co
Co(NH3)4
O
H
5.7.5
65
STEREOCHEMISTRY
Stereochemistry is that branch of chemistry that concerns with the structures of compounds.
Inorganic stereochemistry deals with central atoms having coordination numbers from two to twelve.
6.1
Coordination number 2
Coordination number 2 is confined to complexes of Cu I, AgI, AuI, and HgI. The complexes are all
linear. Examples include ammine complex of AgI,
[NH3 Ag NH3]+, and cyano complex of AgI, [NC Ag CN]-. These ions have d10
configuration. Other examples are [AgCl2]-, [HgCl2], [AuCl2]- and Au(CN)2-.
6.2
Coordination number 3
This is rather rare among metal complexes. Many complexes which appear to be 3-coordinate as
judged by their stoichiometry are found upon examination to have higher coordination numbers. For
examples, Cs[CuCl3] has an infinite chains Cl-CuCl2-Cl-, a coordination number of 4; K[CuCl3] has
an infinite double chains of Cl4-Cu2Cl2-Cl4, a coordination number of 6, having a distorted octahedral
structure; and K[Cu(CN)2] has a chain [-CN-Cu(CN)-CN-Cu(CN)-CN-) and is an example of true 3coordination.
Four other examples of truly 3-coordinate complexes are the triiodomercurate(II) anion, HgI3-,
bis(thiourea)copper(I) chloride, [Cu(tu)2]Cl, tris(trimethylphosphinesulphidecopper(I) perchlorate,
[Cu(SPMe3)3]+ClO4- and tris(triphenylphosphine)platinum(0), [{(Ph)3P}3Pt]0. All the examples
feature ligands with bulky groups.
6.4
Coordination number 4
This coordination number is very common. The structures formed with this coordination number can
be divided into two: tetrahedral and square planar. There are, however, intermediate structures and
distortions.
6.5
Tetrahedral complexes
Tetrahedral structures are not stabilized by large CFSE (see later). The structure is favoured by large
ligands like Cl-, Br-, I- and small metal ions of three types:
Those with a noble gas configuration ns2np6 such as Be2+, MnVII (e.g. MnO4-)
Those with a pseudo-noble gas configuration ns2np6(n-1)d10, such as CuI, ZnII GaIII and Ni0.
Those transition metal ions, which do not strongly favour other structures by virtue of the
CFSE such as CoII, d7.
Specific examples for transition metal ions are MnO4-, Ni(CO)4 and [Cu(py)4]+. Tetrahedral
complexes do not exhibit geometric isomerism, although they are potentially optically active just like
tetrahedral carbon.
Example: bis(benzoylacetonato)beryllium.
6.6
Square planar complexes
They are formed by very few metal ions. The best known are d8 species such as Ni2+, Pd2+, Pt2+, and
Au3+. There are a few complexes of Co2+ (d7) with bidentate ligands that are square planar, but
otherwise such complexes are rather scarce. Chlorophyll and other bio-complexes are important
exceptions to this rule where the geometry is dictated by the rigid porphyrin structure. Square planar
structure is favoured by non-bulky, strong field ligands with sufficiently good -bonders to
compensate for the energy lost through 4- rather than 6-coordination. For example [Ni(CN)4]2- is
square planar whereas Ni2+ forms octahedral complexes with H2O and NH3, and tetrahedral
complexes with Cl-, Br- and I-. For the heavier d8 metals steric requirements are relaxed and the
effective field strength of all ligands is increased. Under such conditions [PdCl4]2-, [PtCl4]2-+ and
[AuCl4]- are square planar.
Account for why Pd2+ and Pt2+ have stronger tendency to form square planar complexes than Ni2+.
66
There is only a small difference in the energy of square planar and tetrahedral complexes. Both
structures can therefore inter-convert easily. A number of Ni2+ complexes do inter-convert readily.
In the M2[CuX4] series of complexes of CuII, variation of MI and X gives complex anions with
stereochemistries ranging from square planar (e.g. (NH4)2 [CuCl4]) to almost tetrahedral (e.g.
Cs2[CuBr4].
Square planar complexes, of the formula [MA2B2], exhibit cis-trans isomerism (see next chapter). If
such complexes are neutral molecules, they may be readily distinguished by the presence of a dipole
moment in the cis isomer but none in the trans isomer.
6.7
Coordination number 5
The structures of 5-coordinate complexes lie between two limiting geometries: trigonal bipyramidal
and square pyramidal. These limiting structures are not markedly different. The conversion of one
structure into other requires a relatively slight distortion.
Square pyramidal
Trigonal bipyramidal
Examples: [CdCl5]3- is almost an ideal trigonal bipyramidal; [NiCl5]3- is almost an ideal square
pyramidal.
6.8
Coordination number 6
This is the commonest and most important coordination number for transition metal complexes. The
geometry usually corresponds to six coordinated atoms at the corners of an octahedron or a distorted
octahedron.
A regular geometry
67
BONDING
7.1
Valence Bond Theory (VBT)
Valence bond theory assumes that bonding in coordination compounds is solely covalent. The
formation of coordinate compounds is described by the hypothetical sequence:
Removal of electrons from the metal to give the appropriate cation.
Hybridization of those atomic orbitals which will provide a set of equivalent hybrid orbitals
directed towards the ligands.
Where necessary, rearrangement of the metals electrons in order to ensure that the hybrid
orbitals are empty.
Formation of covalent bonds by overlap of the hybrid orbitals with the ligand orbitals
containing the lone pair of electrons.
The common types of hybrid orbitals are given below:
Coordination No.
Atomic orbitals
Hybrid orbitals
Geometry
2
spx
sp
Linear
2
3
spxpy
sp
Trigonal planar
4
spxpypz
sp3
Tetrahedral
2 2
2
2
5
spxpydx -y
sp d or dsp
Square planar
6
spxpypzdx2-y2dz2
sp3d2 or d2sp3
Octahedral
[Hybridization is mixing of orbitals to get hybrid orbitals. Hybridization is not a phenomenon, but a
mathematical manipulation. Hybrid orbitals have no physical existence in reality]
Examples
Consider CoII complexes in 4- and 6- coordinate complexes:
3d7
4p0
4s2
Co
Co2+
sp3
XX
XX
XX XX
68
4d0
dsp2
XX
XX
XX
XX
XX XX
XX
XX
XX
XX
d2sp3
XX
XX
XX
XX
XX
XX
? The remaining electron from the CoII ion promoted to an unknown orbital.
Note: Two types of octahedral complexes are apparent: one which uses only 3d orbitals and the other
which makes use of 4d orbitals for bonding. These have been described as covalent or inner
orbital and ionic or outer orbital respectively. In the inner orbital case note the promotion of a
single electron to an unspecified outer orbital. This is in agreement with the case with which Co2+
complexes are oxidized to Co3+.
Secondly the two forms of 6-coordinate and 4-coordinate complexes differ in the number of unpaired,
non-bonding electrons present. Since the magnetic moments of complexes are dependent on the
number of unpaired electrons, magnetic moments can provide useful indications of structure and bond
type.
Shortcomings of the valence bond theory
Other aspects of magnetic behaviours, such as variation of magnetic moment with temperature
are not explained by VBT.
Does not explain origin of colour in transition metal compounds. This is a major shortcoming.
Does not explain why some ligands give rise to high-spin and some to low-spin complexes.
Cannot distinguish two complexes with same number of unpaired electrons but with different
structures.
Examples
1.
Discuss bonding in [Co(NH3)6]Cl3 and [CoF6]3- which are diamagnetic and paramagnetic
respectively.
69
3d
4p
4s
4d
Co
Co3+
[Co(NH3)6]
XX
XX
XX
XX
XX XX
Note that all electrons are paired, hence the complex is diamagnetic.
3d
[CoF6]3-
4s
XX
4p
XX XX
4d
XX
XX XX
Note 4 unpaired electrons, paramagnetic. Magnetic moments can therefore be used to distinguish
between the two complexes.
2.
Consider [Fe(H2O)6]3+ with 5 unpaired electrons and Fe(CN)6]3- with one unpaired
Use the valence bond theory to explain these observations.
electron.
3.
There are three groups of complexes of Ni2+; one group is diamagnetic and
two
are
paramagnetic. By considering 4-coordinate and 6-coordinate
complexes, account for the three
groups of complexes.
7.2
70
eg
Energy
6Dq
/5
o
=10Dq
Baricentre
-4Dq
-2/5
t2g
Free ion
(gaseous state)
Splitting of d-orbital
energies in octahedral
crystal field
The dx2- y2 and dz2 orbitals, which point directly towards the ligands will suffer greater repulsion (i.e.
higher energy) than those orbitals which point between axes. The energies of the d-orbitals split into
two sets: two axial and three non-axial. The axial orbitals are referred to as eg while the non-axial are
t2g. Thus the eg set increases in energy while the t2g set decreases in energy. Their separation is given
the symbol o or 10Dq and referred to as crystal field splitting energy (for octahedral field). The
energy level splitting in an octahedral environment is given at page 26.
The separation between eg and t2g is very important because it introduces the possibility of rearranging the metal d-electrons. The Hunds rule still holds in the sense that d-electrons still tend to
remain unpaired until each orbital is singly occupied before pairing can occur. However, electrons
would tend to occupy the orbitals of lower energy before the eg orbitals are filled, particularly if the
separation energy is large.
eg
Energy
6Dq
/5
Baricentre
-4Dq
-2/5
o
=10Dq
o
t2g
Free ion
(gaseous state)
Splitting of d-orbital
energies in octahedral
crystal field
For d1 to d3 the electrons go singly into the t2g orbitals; however, for d4, d5, d6, and d7 two options are
open, depending on the magnitude of o.
If o is large, i.e. the crystal field is strong the electrons are forced to pair in the lower t2g set
and the configuration is known as spin-paired or low-spin.
If o is small, i.e. the crystal field is weak, the maximum number of electrons remain unpaired
and the configuration is known as spin-free or high-spin.
This is summarized below:
71
d1
d2
d4
d3
d5
high
spin
low
spin
d6
d7
d9
d8
high
spin
low
spin
Note that both low- and high- spin for d9 are the same
These arrangements correspond to the outer orbital and inner orbital types of VBT:
Outer orbital High spin
Inner orbital Low spin
Thus the vacant orbital created to allow for vacant d-orbitals required for hybridization (i.e. d2sp3) in
VBT is equivalent to the empty eg orbital in low-spin configuration in CFT.
For example, Co2+ octahedral complex in CFT would generate two configurations:
72
eg
eg
t2g
t2g
Also note that the electron promoted to unknown orbital in VBT is actually in the eg level in CFT and
that o for high-spin complexes is smaller than o for low-spin.
Other examples:
Use the crystal field theory to account for
(a)
[Fe(H2O)6]3+ having 5 unpaired electrons whereas [Fe(CN)6]3- has one
(b)
7.2.2
unpaired electron.
Bonding in tetrahedral complexes occurs essentially the same way as in octahedral complexes except
that electrons approaching between axis (now t2) will be more strongly repelled than those along axis
(now e). The d-orbital splitting is thus an inverted form of the octahedral.
t2
Energy
/5
Baricentre
t
3
- /5
The separation energy between e and t2 levels is t. Both o and t are called crystal field splitting
energies for octahedral and tetrahedral geometries respectively. For the same metal, at the same
oxidation state, and the same ligands, t -4/9o.
The occurrence of high-spin and low-spin configurations for d3, d4, d5 and d6 ions is also possible in
principle but rather rare to have low-spin tetrahedral complexes because of the small crystal field
splitting energy involved.
Reasons why t is smaller than o
Four ligands are involved in tetrahedral complexes as against six in octahedral. Larger crystal
field is therefore expected for six ligands than for four.
The ligands in tetrahedral complexes are less efficiently directed (between axes) than they are
in octahedral (along axes). The ligands are therefore not aimed at any of the orbitals but exert
a somewhat larger influence on the t2g orbitals than the eg orbitals.
73
7.2.3
The square-planar geometry is usually conceived as an octahedral complex where the axial ligands
have been elongated to infinity (i.e. totally removed). The effect of this is to reduce the energy of the
dz2 orbital (which points along the vertical axis). This would have the effect of lowering the energy of
the dxz
dx2-y2
dxy
dz
dxz, dyz
Square-planar
Octahedral
n+
L
L
n+
n+
x
L
Octahedral
complex
Removal of axial
ligands
Square-palnar
complex
and dyz orbitals of the t2g level; that is the degeneracy of the eg and t2g levels
are removed.
In the square-planar complexes of the d7 ion, Co2+, and the d8 ions, Ni2+, Pd2+, and Pt2+, electrons are
forced to pair in the lower four orbitals, leaving the top dx2-y2 orbital vacant. In the VBT this orbital is
used for bonding. (Remember dsp2 hybridization?)
7.3
The ligand field theory (LFT)
LFT is a modified CFT which allows the possibility of covalent bonding in addition to electrostatic
bonding in the formation of metal complexes. This theory can account, at least qualitatively, for the
crystal field splitting caused by various ligands. Ligands like CO, CN-, phen, and NO2- which provide
the largest crystal fields, are all able to form bonds with the central metal ion/atom. This bonding
markedly increases the magnitude of o.
74
The magnitude of o is also strongly influenced by the oxidation state of the metal ion and the type of
d electrons present. The higher the oxidation state of the metal ion the larger the crystal field splitting.
For example, [Co(NH3)6]3+ is diamagnetic; [CoF6]3- is paramagnetic. Ions with high charge and small
sizes can be approached more strongly by ligands than larger cations of smaller charge.
It is also known that the greatest crystal field splitting is observed in complexes of 5d metals and
decreases from 4d to 3d. Thus o([Ir(NH3)6]3+) > o([Rh(NH3)6]3+) > o([Co(NH3)6]3+)
The arrangement of the ligands in the order of the magnitude of their o is known as the
spectrochemical series and follows the order:
Weak field ligands
Intermediate field ligands
- I <Br <Cl <OH <RCO2 ,F < Ox-<H2O<NH3<en<
To account for this order the extreme assumption of pure covalency in the VBT and pure electrostatic
model of CFT must be abandoned for the existence of both modes of bonding in metal complexes.
Values of o for selected metal complexes
Complex
[TiF6]3[Ti(H2O)6]3+
[V(H2O)6]3+
[V(H2O)6]2+
[CrF6]3+
[Cr(H2O)6]3+
[Cr(H2O)6]2+
[Cr(NH3)6]3+
[Cr(CN)6]3[MnF6]2[Fe(H2O)6]3+
[Fe(H2O)6]2+
/cm-1
17 000
20 300
17 850
12 400
15 000
17 400
14 100
21 600
26 600
21 800
13 700
9 400
Complex
[Fe(ox)3]3[Fe(CN)6]3[Fe(CN)6]4[CoF6]3[Co(NH3)6]3+
[Co(NH3)6]2+
[Co(en)3]3+
[Co(H2O)6]3+
[Co(H2O)6]2+
[Ni(H2O)6]2+
[Ni(NH3)6]2+
[Ni(en)3]2+
/cm-1
14 100
35 000
33 800
13 100
22 900
10 200
24 000
18 200
9 300
8 500
10 800
11 500
Colour
8.1
Origin of colour
Colour in metal complexes arises from
Transitions between metal-centred orbitals possessing d-character (d-d transitions).
Transitions between metal- and ligand-centred MOs which transfer charge from metal-toligand or ligand-to-metal (charge-transfer transitions).
8.2
Selection rules
Electronic transitions obey the following selection rules:
Spin selection rule: S = 0
Transitions may occur from singlet to singlet, or triplet to triplet states and so on, but a change in spin
multiplicity is forbidden.
Laporte selection rule: There must be a change in parity:
allowed transitions: g u
forbidden transitions: g g and u u
75
1 = c
Absorption bands are described in terms of max corresponding to the absorption Amax. The unit of
is nm while that of wavenumbers is cm-1. If the electronic spectrum is done in a solution, the
extinction coefficient max of the absorption must also be reported. max indicates the intensity of the
absorption and is related to Amax.
Rh
>
Co
41 000
34 000
23 000 cm-1
Greatly on the nature of the ligand. increases along the spectrochemical series: I- < Br- < Cl< F < OH- < Ox- < H2O < NH3 < en < phen < NO2- < CN-
Charge-transfer transition
The separation of d-orbitals into t2g and eg levels translates into making the t2g orbitals more stable and
the eg orbitals less stable than the degenerate orbitals. Consequently a t2g electron increases the
stability of an octahedral complex by 2/5o and an eg electron decreases it by 2/5o. The net effect of
all the d electrons represents the additional stability which may be thought to accrue because the CF
splits the d-orbitals. This is known as Crystal Field Stabilization Energy, CFSE. This extra stability
reflects in experimental values of such thermodynamic quantities as hydration energies, lattice
energies, and standard reduction potentials. The most complete set of data is the hydration energies of
bivalent ions: the experimental values of Ho lie on an irregular double-humped curve.
If the CFSE is, in each case, subtracted from Ho, the corrected values fall very neatly on a smooth
curve, passing through the points for the spherically symmetrical d0, d5, and d10 ions. CFSE,
therefore, offers a ready explanation of the Irving-Williams order of stability, MnII < FeII < CoII < NiII
< CuII > ZnII.
9.1
Calculation of CFSE
A total crystal field stabilization energy is calculated by adding up the Dq energies for each electron
after the low-spin or high-spin configuration has been established.
Example: Calculate the CFSE for Cr3+ and Fe3+ ions.
Draw the crystal field energy level diagrams for each and in the case of Fe 3+, draw for both low-spin
and high-spin configurations before calculating the CFSEs.
CFSE = [6Dq (No. of electrons in the eg level)]+[-4Dq (No. of electrons in the t2g
77
level)]
level)]
Cr3+, d3 ion:
+6Dq
-4Dq
CFSE = 6 Dq x 0 -4 Dq x 3 = -12 Dq
+6Dq
+6Dq
-4Dq
-4Dq
Weak field
Strong field
For weak field
CFSE = 6 Dq x 2 4 Dq x 3 = 12 Dq 12 Dq = 0 Dq
For strong field
CFSE = 6 Dq x 0 4 Dq x 5 = -20 Dq
The lower the CFSE, the more stable the complex. Thus low-spin Fe3+ is more stable than high-spin
Fe3+. Also low-spin Fe3+ ion is more stable than Cr3+ ion.
10
A regular octahedral environment is the most stable one for a spherically symmetrical metal ion
surrounded by six donor atoms. For metal ions with certain d electron configurations which are not
spherically symmetric, the regular octahedral configuration is not the most stable. This situation is
expressed in Jahn Teller theorem: Any non-linear molecule that is in an electronically degenerate
state will undergo distortion to lower the symmetry, remove the degeneracy, and lower the energy.
Jahn Teller distortion occurs strongly in all cases where the eg level is not uniformly occupied by
electron. Much weaker distortion also occurs if the t2g level is not uniformly occupied.
In the case of eg, any odd electron can occupy either the dz2 or the dx2-y2 orbital. If, however, the
complex undergoes distortion the eg level is split and the electron can occupy the lower of the two
orbitals (the dz2 orbital in the case of tetragonal elongation, or the dx2-y2 orbital in the case of tetragonal
compression).
In tetragonal elongation the ligands on the z axis move out and therefore interact less with those
orbitals which have a z component; i.e. the dz2, dxz, and dyz, and these orbitals attain lower energy (i.e.
78
stabilized). Those orbitals without a z component, i.e. dx2-y2 and dxy, will be raised a corresponding
amount.
Compression: dx2-y2 attains lower energy
2 2
-y
dx
L
a
L
2
dz
dxy
dxz, dyz
1 band
3 possible bands
L
dx2-y2
a
L
L
dxz, dyz
L
dxy
1 band
3 possible bands
Consequently an ion which is susceptible to Jahn Teller distortion could produce additional bands
(maximum of three altogether). Some of the additional bands may often appear as shoulders,
depending upon the magnitude of the distortion.
Configurations d4, d7, and d9 are the most distorted. In high-spin d4, low-spin d7, and d9 the eg level is
not evenly occupied and are therefore susceptible to strong Jahn Teller distortion.
Uneven occupation of the t2g orbitals also results in distortion but much weaker than in uneven
occupation of eg orbitals. Thus Ti3+, d1- is less distorted than Cu2+, d9.
Relatively weak distortions are expected for tetrahedral complexes with d3, d4, d8, and d9
configurations. Why?
Other evidences of Jahn Teller distortion
IR can usually detect weakening of ML bonds as a result of distortion.
X-ray structure would reveal unusually long or short bond lengths.
11
Most measurements of stability are done in aqueous solutions when the complex in question is formed
by a ligand displacing water from the aquo complex of the metal ion. Metal complexes are formed in
solution by stepwise reaction, and equilibrium constants can be written for each step. For example,
+
[Ag(H2O)x]+
[Ag(NH3)(H2O)x-1] + H2O
k1
+
[Ag(NH3)2(H2O)x-2] + H2O
[Ag(NH3)(H2O)x-1] + NH3
k2
For simplicity we can ignore the water molecules that make up the hydration sphere of an aqueous
metal ion. Moreover, the solvent water molecules involved in the reaction are not included in the
equilibrium constants, k1 and k2 above are called stepwise-wise stability constants.
+
k1 =
[Ag(NH3) ]
k2 =
[Ag ][NH3]
[Ag(NH3)2 ]
[Ag (NH3)+][NH3]
The larger the value of the constant, the greater the concentration of the complex species at
equilibrium. A second type of equilibrium constant, , called an overall stability constant can be
defined for the reactions above:
+
+
[Ag(NH3)2 ]
[Ag(NH3) ]
;
=
+
[Ag +][NH3]2
[Ag ][NH3]
Since the ks and s describe exactly the same chemical systems, they must be related to each other:
+
[Ag(NH3)2 ]
+
[Ag ][NH3]
[Ag(NH3)2+]
[Ag +][NH3][NH3]
[Ag(NH3)2+]
[Ag(NH3)+]
+
[Ag(NH3) ]
+
[Ag(NH3) ]
= k2 . k1
Note that 1 = k1 and 2 = k2 . k1. By similar treatment it can be shown that
n = k1 k2 k3 ..kn.
The numerical value of stability constant describes the relative concentration of species at
equilibrium. Large stability constants indicate that the concentration of a complex is much greater
than the concentration of the components it is made.
A complex is said to be stable if the equilibrium constants describing its formation is large.
10.1
The equilibrium constant of a reaction is a measure of heat released in the reaction and the entropy
change during the reaction.
-RT lnk = G = H TS
The larger the heat evolved in a reaction the more stable are the reaction products. The following
factors affect stabilities of complexes:
The metal ion and its charge. For example, M3+ complexes are more stable than M2+. Recall:
Mn2+<Fe2+<Co2+<Ni2+<Cu2+>Zn2+, which is the reverse of the order for the cation sizes.
The relationship between metal and donor atoms. Class-a acceptors or hard acids (metals in
Group IA and IIA along with the inner transition metals and the early members of the first row
transition metals) form their most stable complexes with ligands containing O, N or F donor
atoms. Class-b acceptors or soft acids (other metals form their most stable complexes with
ligands containing heavier members of N, O, and F groups). For example, Rh, Pd, Ag, Ir, Pt,
80
Au and Hg are class-b acceptors. The remaining transition elements are regarded as
borderline.
The types of ligands. Bidentate ligands form more stable complexes than monodentate ligands
due to chelate effect. Chelate effect is stabilized due to chelation. The chelate rings of 5 and
6 are more stable. The stability of a metal chelate is greater than that of an analogous nonchelated metal complex. For example, the stability of [Ni(en)3]2+ is greater than that of
[Ni(NH3)6]2+. The more extensive the chelation the more stable the system.
Ligand
NH3
logks
logk1
logk2
logk3
logk4
logk5
logk6
logk1
logk2
logk3
logk1
logk2?
logk1
en
trien
6-en
trien = diethylenetetramine
NH2
Co2+
2.1
1.6
1.1
0.8
0.2
-0.6
6.0
4.8
3.1
8.1
Ni2+
2.8
2.2
1.7
1.2
0.8
0.03
7.5
6.3
4.3
10.7
Cu2+
4.2
3.5
2.9
2.1
-0.5
10.6
9.1
-1.0
16.0
Zn2+
2.4
2.4
2.5
2.2
5.7
4.7
1.7
8.9
15.8
19.3
22.4
16.2
6-en = pentaethylenehexamine
H2N
= H2NCH2CH2(NHCH2CH2)4CH2CH2NH2
NH
HN
Why is Co2+<Ni2+<Cu2+>Zn2+?
Why 6 NH3, 3 en, 2 trien and one 6-en?
Why is logk1 > logk2 > logk3> ?
Why is logk6 for [Co(NH3)6]2+ negative?
Why is logk5 and logk6 negative or non-existent for [Cu(NH3)6]2+?
Why is log6 (for NH3 complexes) < log3 (for the en complexes) < log1 (for 6-en complexes) in
each metal?
For steric reasons large bulky ligands form less stable metal complexes than do analogous smaller
ligands. For example H2NCH2CH2NH2 forms more stable complexes than (CH3)2NCH2CH2N(CH3)2.
Examples:
Complex
[Ni(NH3)6]2+
[Ni(en)3]2+
[Ni(dien)2]2+
1
5 x 102
2
6 x 104
3
3 x 106
1
5 x 107
4
3 x 107
2
1.1 x 1014
1
6 x 1010
5
1.3 x 108
3
1.4 x 1018
2
8 x 1018
dien = H2NCH2CH2NHCH2CH2NH2
81
6
1.0 x 108
82
SECTION D
ORGANOMETALLIC CHEMISTRY
(METAL CARBONYLS)
83
ORGANOMETRALLIC CHEMISTRY
Definitions:
Organometallic compounds are compounds that possess one or more metal-carbon bond.
The bond must be ionic or covalent, localized or delocalized between one or more carbon
atoms of an organic group or molecule and a transition, lanthanide, actinide, or main group
metal atom.
Organometallic compounds are very important in the chemical industry, as a number of them
are used as industrial catalysts and as a route to synthesizing drugs that would not have been
possible using purely organic synthetic routes.
Coordinative unsaturation is a term used to describe a complex that has one or more open
coordination sites where another ligand can be accommodated.
Hapticity of a ligand is the number of atoms that are directly bonded to the metal centre.
Hapticity is denoted with a Greek letter (eta) and the number of bonds a ligand has with a
metal centre is indicated as a superscript, thus 1, 2, 3, n for hapticity 1, 2, 3, and n
respectively.
Bridging ligands are normally preceded by , with a subscript to indicate the number of metal
centres it bridges, e.g. 2CO for a CO that bridges two metal centres.
Ambidentate ligands are polydentate ligands that can coordinate to the metal centre through one or
more atoms.
For example CN can coordinate via C or N; SCN via S or N; NO2 via N or N. The term
can also be used to describe instances where a ligand can behave as monodentate or a
chelating ligand.
Bite angle is the ligandmetalligand angle formed when a polydentate ligand coordinates to a metal
centre.
A Chelate (Greek word for claw is a polydentate ligand that forms a ring that includes a metal.
Examples are EDTA, acac, en.
Heterobimetallic describes a complex in which there are two different metal centres.
Homobimetallic complexes have two metal centres that are the same elements. These need not have
identical ligands or coordination number, but are usually found as symmetric dimers.
Homoleptic complexes are compounds in which all the ligands that bound to the metal centre are
identical.
A ligand is a molecule or ion that is bonded directly to a metal centre, usually by a covalent or
coordinate bond.
84
Monodentate ligands have only one point of attachment to the metal centre and occupy one
coordination site only. Examples of monodentate ligands are NH3, CO, NMe3, H2O and PMe3.
Polydentate ligands have more than one point of attachment to the centre and occupy more than one
coordination site.
By definitions above bidentate ligands and ambidentate ligands are special cases of
polydentate ligands.
The primary coordination sphere of a metal involves the set of ligands closest to the metal that are
directly bonded. Mobile cations and anions are said to be in the outer or secondary sphere.
Zeises salt:
Na[PtCl3(C2H4)]
1849
Frankland:
[(C2H5)2Zn]
1890
Mond:
1931
Hieber:
1951
Ferrocene:
BONDING
Bonding is essentially covalent and can be MetalCarbon (as in metal carbonyls and
alkyls) or MetalCarbon bonds (as in metal alkenes, alkynes and arenes).
Ionic compounds are often formed with electropositive metals, e.g. (C6H5)3C-Na+ and (C5H5
)2Ca2+. These ionic compounds are insoluble in hydrocarbon solvents and are very sensitive
to air and moisture.
ELECTRON COUNTING
The 18-electron rule
The 18-electron rule is like the octet rule to the organometallic chemists.
18-electron rule is also known as the effective atomic number rule (EAN rule).
The rule is used to determine the number of valence electrons in a complex to determine
whether that complex is likely to be stable or not.
85
18 electrons arise from electrons from completely filled five d, three p, and one s orbitals.
A stable complex is obtained when the sum of metal d-electrons, the electron donated from
the ligands, and the overall charge of the complex equals 18.
These are just two different methods of an accounting system that give the same final answer.
All you need to do is to understand one and keep to that to avoid confusion.
When a metal ion is put into an electronic field (surrounded with ligands), the d-orbitals drop
in energy and fill first.
The organometallic chemist therefore, considers the transition metal valence electrons to be
all the d-electrons.
Thus a transition metal such as Ti in the zero oxidation state attains a d4, and not d2
configuration.
Thus for zero-valent metals, the electron count simply corresponds to the column it occupies
in the periodic table. Fe, for example, in the 8th column is d8 and not d6; Re3+ is d4 (seventh
column for Re, and then add 3 position charges or subtract three negative ones).
For example, if we remove ammonia from a complex, NH3, has a completed octet and acts as
a neutral molecule. When it bonds to the metal centre if does so through its lone pair (in a
classic Lewis acid-base sense) and there is no need to change the oxidation state of the metal
to balance charge.
In contrast, if we remove a methyl group from the metal and complete its octet, then we
formally have CH3.
86
If we bond this methyl anion to the metal, the lone pair forms one metal-carbon bond and the
methyl group acts as a 2-electron donor ligand.
To keep charge neutrality we must oxidize the metal by one electron (i.e. assign a positive
charge to the metal). This, in turn, reduces the d-electron count of the metal centre by one.
The methyl group is, therefore, a one-electron donor, not a two-electron donor as it is under
the ionic formation.
Notice that this method does not give us any immediate information about the oxidation state
of the metal, so we must go back and assign that later.
Some commonly encountered ligands donate the following numbers of valence electrons.
1-electron donor: H (in any bonding mode), and terminal Cl, Br, I, R (e.g. R = alkyl or Ph)
or RO;
2-electron donor: CO, PR3, P(OR)3, R2C=CR2 (2-alkene), R2C: (carbine);
3-electron donor: 3-C3H5 (allyl radical), RC (carbine), -Cl, -Br, -I, -R2P;
4-electron donor: 4-diene, 4-C4R4 (cyclobutadienes);
5-electron donor: 5-C5H5, 3-Cl, 3-Br, 3-I, 3-R2P;
6-electron donor: 6-C6H6 (and other 6-arenes, e.g. 6-C6H5Me);
1- or 3-electron donor: NO
Counting electrons provided by bridging ligands, metal-metal bonds and net charges requires care.
When X (X = CI, Br, I) or R2P the ligand uses the unpaired electron and a lone pair to bridge
two metal centres, i.e. one electron is donated to M, and two to the second metal, M
In a doubly bridged species such as (CO)2Rh(-Cl)2Rh(CO)2 the -Cl atoms are equivalent as
are the Rh atoms, and the two Cl bridges together contribute three electrons to each Rh.
A bridging H provides only one electron in total, shared between the metal atoms it bridges,
e.g. [HFe2(-CO)2(CO)6].
MM single bond provides each M atom with one extra electron; an M=M double bond
contributes two electrons to each metal.
87
1.
2.
3.
4.
Consider a MM to provide one electron to each metal; an M=M bond to provide two
electrons to each metal.
5.
Consider bridging two-electron ligands such as CO, CR2 to contribute one electron to each
metal.
2.
CH3
H3C
CH3
(Me3Si)2HC
H3C
CH3
Cr
CH(SiMe3)2
Ti
H3C
CH3
CH3
H3C
(Me3Si)2HC
9 VE
CH3
14 VE
3.
Many organometallic compounds obey the 18-electron rule, but classical coordination
compounds often have widely differing electron counts. Why?
88
With 6 -donor ligands and the metal t2g and eg levels, three classes of complexes can
be seen:
Class I: is small: valence electron (VE) is less than or greater than 18. T2g is nonbonding, eg is weakly antibonding. 1222 VE can be accommodated.
e.g.:
[TiF6]2
[Mn(CN)6]3
[Co(NH3)6]2+
[Zn(en)3]2+
TiIV, d0
MnIII, d4
CoII, d7
Zn2+, d10
12 VE
16 VE
19 VE
22 VE
Class II: M is 2nd/3rd row transition metal and is larger. VE is less than or equal to
18. T2g is nonbonding and occupied with 0-6 electrons, eg is antibonding and
unoccupied.
e.g.:
WVI, d0
WIV, d2
PtIV, d6
PtII, d8
WCl6
WCl62
PtF62
PtCl42
12 VE
14 VE
18 VE
16 VE
Class III: large; VE = 18. These are organometallic complexes. T2g becomes
bonding and is fully occupied, eg is antibonding and empty. The 18-electron rule is
obeyed as far as steric constraints will allow.
e.g.:
V(CO)6
Fe(CO)5
cpCo(CO)2
Ni(COD)2
V, d6
Fe0, d8
Co1, d8
Ni0, d8
18 VE
18 VE
18 VE
18 VE
Examples:
Rationalize the following: Cr(CO)6, Ni(PF4)4, Fe(CO)4PPh3 and Mn2(CO)8
Answer:
Cr
6CO
6e
12e18e-
Ni
4PF3
Fe
4CO
Ph3P
10e
8e18e-
8e8e2e18e-
-BONDING LIGANDS
1.
2.
Metals that could form complexes with the above ligands display low positive, zero, or
negative formal oxidation states.
Properties of complexes:
These ligands then stabilize low oxidation states.
This property is associated with the fact that in addition to lone pairs of electrons, the
ligands possess vacant -orbitals, which accept electrons density from filled metal orbitals
3.
89
fo form a type of -bonding that supplements the -bonding arising from lone-pair
donation.
The ability of ligands to accept electron density is then called -acidity (from Lewis
sense).
In this introductory lecture, we will limit ourselves to complexes of carbon monoxide.
Carbon monoxide is not ordinarily considered a very strong Lewis base and yet it forms strong
bonds with the metals it complexes with.
The metals are always in low oxidation state, usually 0, but sometimes +1 or -1.
The 18-electron rule is obeyed by at least 99% of all the organometallic complexes.
Examples of stable carbonyl complexes of the first row transition metals are given in the Table
below.
Mononuclear V(CO)6
Dinuclear
Trinuclear
Tetranuclear
Hexanuclear
Cr(CO)6
Mn2(C0)10
Fe(CO)5
Fe2(CO)9
Fe3(CO)12
Ni(CO)4
Co2(CO)8
Co4(CO)12
Co6(CO)16
The only exception to the 18-electron among the mononuclear carbonyl complexes is
hexacarbonylvanadium(0), V(CO)6, which is paramagnetic and is a 17-electron molecule.
V(CO)6 does not dimerise to give the 18-electron analogue like Mn2(CO)10 and Co2(CO)8
because each metal would attain a coordination number of 7, which may present too much
steric hindrance to allow stability.
This may also be due to ligand repulsion that can overcome weak MM bond or present a
kinetic barrier to dimerization.
V(CO)6 is, however, less stable than other carbonyl complexes that obey the 18-electron rule.
It decomposes at 70 and readily forms [V(CO)6] to form the 18-electron anion.
The tendency to form more complex carbonyls increases from left to right in the first row
transition metal series.
Second and third-row transition metals form parallel complexes to the ones given in the table
above; e.g. Mo(CO)6, Tc2(CO)10 and Re2(CO)10
90
Generally the carbonyls of the first row transition metals are more stable than their analogues
in the second and third row series. For example, Fe(CO)5 > Ru(CO)5 > Os(CO)5; Fe2(CO)9 >
Ru2(CO)9 > Os2(CO)9.
Increasing strength of MM interaction as one descends the transition metal series leads to
enhanced stability for Os3(CO)12 and Ru3(CO)12 relative to the mononuclear, M(CO)5.
From the metal: By direct action of CO on finely divided metal. Only [Ni(CO)4] and
[Fe(CO)5] are so made.
Ni + 4 CO
25oC
1 bar
[Ni(CO)4]
o
Fe + 5 CO 150 C [Fe(CO)5]
100 bar
[Ni(CO)4] is a highly toxic colourless liquid; b.p. 34 oC. Purification of nickel by Monds
process is attained by decomposing [Ni(CO)4].
[Fe(CO)5] is a yellow liquid; b.p. 103 oC. [Fe(CO)5] is very sensitive to light and heat and
decomposes in air.
Photolysis of [Fe(CO)5] yields an orange yellow solid [Fe2(CO)9].
[Fe(CO))5]
(b)
CrCl3 + Al
benzene, AlCl3
300 bar CO
Mn(OAc)2 + 10 CO
[Cr(CO)6] + AlCl3
AlEt3, PriO
[Mn2(CO)10]
[Cr(CO)6] is colourless, diamagnetic, air-stable solid; m.p. is 154 oC. It has18 VE.
[Mn2(CO)10] is a yellow crystalline, diamagnetic solid. It also obeys 18-electron rule.
2 CoCO3 + 2 H2 + 8 CO
300 bar CO
130 oC
300 bar CO
130 oC
91
CO
CO
OC
CO
OC
CO
Co
M
CO
OC
OC
CO
OC
Solid state
OC
OC
CO
CO
CO
Co
OC
CO
Mn
OC
Co
CO
M = V, Cr, Mo, W
OC
CO
CO
OC
CO
Co
OC
Mn
CO
CO
CO
CO
OC
CO
Solution
Group 8
OC
CO
Group 9: M = Co, Rh
M
OC
CO
OC
COCO
Ir
CO
OC
M = Fe, Ru, Os
OC
OC
O
C
OC
OC
Fe
Fe
OC
CO
CO OC
CO
OC
Fe
Fe
CO
OC
M
CO
CO
CO
CO
CO
OC
OC
CO
Ir
Ir
CO
OC
OC
OC
M
CO
CO
CO
CO
M
CO
CO
CO
M
O
C
CO
CO
Ir
OC
OC
CO
OC
OC
CO CO
Fe
OC
C
O
OC
OC
CO
CO
M
CO
CO
CO
CO
M = Ru, Os
O:
-bond
:C
:C
-bond (ML)
The * orbital accepts electron density from an occupied d-orbital. CO is therefore a strong -acid
This process is known as back-bonding. MC Bond strengthened; CO bond weakened
Both processes operate in opposite directions but are supportive i.e. Synergic bonding
The bonding mechanism is synergic, because back-bonding will tend to make the CO as a whole
negative (increasing its basicity); at the same time the electron drift to the metal in the -bond tends to
make the CO positive. In other words, the two effects assist each other.
The bond-order for MCO bond is therefore greater than 1 but less than 2.
Physical evidence for bond-order/strength of MCO bond
Dipole moment of an MC bond is very low (0.5 D)
Bond length: Shorter MC and longer CO bonds as compared to single and triple bonds;
CO bond is 1.128 , while in metal carbonyl complexes it is 1.15 .
Vibrational spectroscopy (studying CO stretching frequencies): see below.
COORDINATION MODES OF CO
O
O
O
O
C
free
C
M
terminal
doubly
bridging
CO
2143
2120-1850
1850-1750
93
M
M
triply
bridging
1730-1620 cm-1
CO
OC
CO
Cr
OC
CO
CO
OC
OC
CO
octahedral
CO
CO
Mn
CO
Mn
OC
CO
CO
CO
octahedral
CO = 2000 cm
-1
OC
CO
Fe
CO
CO
Ni
OC
OC
CO
CO
CO
tetrahedral
CO = 2057 cm-1
trigonal bipyramid
CO = 2034, 2013 cm-1
INFRARED SPECTROSCOPY
As mentioned above, the stretching frequency (CO) of the carbonyl bond can be very characteristic
and can be used to establish the mode of bonding of the gas. A number of factors determine the
stretching frequency of CO in any mode of bonding.
(i) Influence of charge
d10
d6
[Ni(CO)4]
[Co(CO)4]
[F2(CO)4]2
[Mn(CO)6]+
[Cr(CO)6]
[V(CO)6]
CO (cm-1)
2060
1890
1790
2090
2000
1860
As neutral, volatile molecules, mass spectrometry is useful to observe parent molecular ions.
In addition, a sequential loss of carbonyl ligands can be seen and aids characterization.
C
C
O
CO bridges often occur in pairs and can be in equilibrium with the non-bridging mode e.g.
O
C
O
CO CO
CO
C
OC
OC
CO
Co
Co
Co
Co
Co
CO
CO
C
O
C
O
C
O
CO
C
O
D3d
C2V
(in solution)
+CO
L'
LnM
LnM - L'
vacant
coordination
site
Second row complexes usually react faster than first- or third- row analogues.
(Some substitution reactions (typical) are shown in figure 7)
Photochemical substitution involves mild reaction conditions and allows synthesis of highly
substituted or more labile products.
95
Co2(CO)8
hv
18VE
2 Co(CO)4.
17VE
Co2(CO)7L
18VE
product
Na[H Fe(CO)4]-
Fe(CO)5 + NaOH
NaH
Na2[Fe(CO)4]2Co2(CO)8 + 2 Na
THF
2 Na+[Co(CO)4]-
Carbonyl metallates are strong bases/nucleophiles and basicity increases within a group.
First < second < third
96