One minute) are said to be labile whereas those that take much longer are called inert.

The two common period 4 transition metal ions that from inert complexes are
chromium(III) and cobalt(III). The former has a d3 electron configuration and the latter, a low
spin d3 configuration (figure 18.37) it is the stabilityof the half-filled and the filled lower set of d
orbitals that precludes any low-energy pathway of reaction. For example, addition of
concentrated acid to the hexaamminecobalt(III) ion shuld cause a ligand replacement according
to free energy calculations. However, such a reaction occurs so slowly that several days must
elapse before any color change is noticeable:

For this reason, for synthezise specific cobalt(III) or chromium (III) complexes, we usually find
a pathway involves synthesizing the complex of the respective labile 2+ ion and then oxidizing it
to he inert 3+ ion.

Coordination Complexes and the HSAB Concept

Just asthe HSAB cocept can help us predict main group reactions (as we saw in chapter 8), so it
can help us understand the ligand preferencesof transition metals in different oxidation states.
Table 18.4 shows the qualitative divisions into hard/borderline/soft acids of some of the first now
transition elements while figure 18.38 shows the similar divisions ligand atoms into
hard/borderline/soft. These ligand-atom categories generally apply, irrespective of the other
atoms of the ligand. For example, all nitrogen-donor ligands of the form NR3 are hard bases,
where R is an alkyl group such as methyl or hydrogen. Coverselly, all carbon-donor ligands,
such as carbon monoxide and cyanide, are soft bases. Chloride is regarded as hard base, but not
as hard as fluoride or an oxygen-donor ligand. Hence it is depicted in figure 18.38 as half white
and half-shaded.
The HSAB concept accounts for the fact that high oxidation states of metal ions (hard
acids) are found with fluoride or oxide ligands (hard bases). It is the low oxidation states (soft
acids) that are stabilized by such ligands as the carbon-bonded carbonyl (a soft base). To provide
a spesific example, copper(II) fluoride is known, whereas copper (I) fluoride is not; coversely
Table 18.4 some common first row transition metals ions categorized according to the
HSAB concept
Hard Borderline Soft
Ti4+, V4+, Cr3+ Fe 2+, Co 2+, Ni 2+, Cu 2+ Cu +
Mn2+, Mn4+, Mn7+ All metals with 0 or negative
Fe3+, Co3+ oxidation states
 Copper(I) iodides is known whereas copper(II) iodide is not. We can use this principle to
help us synthezise to help us synthezise transition metal compounds in which the metal ions have
abnormal oxidation states. For example, iron is usually found in +2 and +3 oxidation states. We
can prepare a compound of the hard-acid iron(VI) using the hard-base oxide ion to give the
ferrate ion, [FeO4]2-. Similarly, we can prepare a compound of soft-acid iron(0) using the soft-
base carbonyl molecule to give pentacarbonyliron(0), Fe(CO)5.
The HSAB concept is also relevant to ractions of transition metal complexes. In
particular, there is a general tendency for a complex ion to prefer ligand atoms of the same type.
Thus a complex with some hard-base ligands will prefer to add another hard-base ligand.
Similarly, a complex with soft-base ligands will prefer to add another soft-base ligand. This
preference for ligands of the same HSAB type is known as symbiosis.
Cobalt(III) chemistry is particularly useful for the illustration of symbiosis. For example,
the complex [Co(NH3)5F]2+ is much more stable in aqueous solution than [Co(NH3)5I]2+. This
can be explained in HSAB terms by considering that Co(lll) is “hardened" by the presence of
five hard-base ammonia ligands. Thus the soft-base iodide ion in comparatively easily replaced
by water (a hard base ligand) to form [Co(NH3)5(0H2)]2+. On the other hand, [Co(CN) 5l]3+ is
more stable in water than [Co(CN) 5F]3+. It is argued that the five soft-base cyanide ions “soften”
the cobalt(III) complex, resulting in a preference for the soft-base iodide at the sixth coordination
site rather than the hard base water molecule.

A particularly interesting example of the application of the HSAB concept to transition metal
complexes involves linkage isomerism. The thiocyanate ion, NCS-, can bond through the
nitrogen atom, in which case it acts as a borderline base, or through the sulfur atom, in which
case it behaves as a soft-base. We find that in the pentamminethiocyanatocobalt(III) ion,
[Co(NH3)5(NCS)]2+, it is bonded through nitrogen, as we would expect, for the other ligands are
hard bases, While in the pentacyanothiocyanatecobalt(III) ion, [Co(CN)5(SCN)]3-, coordination
is through the lulfur as is consistent with the other ligands, cyanides, being soft bases.

Biological Aspects
The chelate effect is important in biological complexes. There is a tetradentate ligand of
particular importance to biological systems-the porphyrin ring. The basic structure of this
complex is shown in Figure 18.39. It Is an organic molecule In which alternating double bonds
hold the structure in a rigid plane with four nitrogen atoms oriented toward the center. The space
in the center is the right size for many metal ions.
In biological systems, the porphyrin ring carries different substituents on the edge of the
molecule, but the core-a metal ion surrounded by four nitrogen atoms-is consistent throughout
the biological world. Plant life depends on the chlorophylls, which contain magnesiumporphyrin
units, for the process of photosynthesis. Animal life depends upon several metal porphyrin
systems such as the hemoglobin molecule, used for oxygen transport, which contains four iron-
porphyrin units. Thus the porphyrin metal complexes are among the most important in the living
world.
EXERCISES
18.1 Define the following term: (a) transition metal; (b) ligand: (C) crystal field splitling.
18.2 Define the following term: (a) coordination number; (b) chelate; (c) chelate effect.
18.3 Nickel forms two tetracyano complexes, [Ni(CN)4]2- and [Ni(CN)4]4-. Explain why you
might expect complexes with nickel in both normal (+2) and low (0) oxidation states.
18.4 Suggest why the fluoride in which chromium has its highest oxidation state is CrF6 whereas
the highest oxidation state chromium assumes in a chloride is CrCI4.
18.5 In addition to the two geometric isomers of [Pt(NH3)2Cl2], there is a third isomer. It has the
same empirical formula and square-planar geometry, but it is electrically conducting in solution.
Write the structure of the compound.
18.6 Identify the probable type of isomerism for (a) Co(en)3Cl3; (b) Cr(NH3)3Cl3.
18.7 Draw the geometric and optical isomers for the [Co(en)2Cl2]+ ion.
18.8 Provide systematic names for each of the following compounds: (a) Fe(CO)5; (b) K3[CoF6],
(c) [Fe(OH2)6 ]Cl2; (d) [COCI(NH3)4]SO4
18.9 Provide systematic names for each of the following compounds: (a) (NH4)2 [CuCl4];
(b) [Co(NH3)5(0H2)]Br3; (c) K3;[Cr(CO)4]; (d) K2[NiF6]; (e) [Cu(NH3)4](CIO4)2.
18.10 Deduce the formula of each of the following transition metal complexes:
(a) hexaamminechromium(III) bromide
(b) aquabis(ethylenediammine)thiocyanatocobalt (III) nitrate
(c) potassium tetracyanonickelate(II)
(d) tris(1 ,2-diaminoethane)cobalt(III) iodide
18.11 Deduce the formula of each of the following transition metal complexes:
(a) hexaaquamanganese(ll) nitrate
(b) palladium(II) hexafluoropalladate(IV)
(c) tetraaquadichlorochmmium(III) chloride dihydrate
(d) potassium octacyanomolybdenate)(V)
18.12 Write the names of the following geometric Isomers:

18.13 Werner's student, Edith Humphrey, was the first to synthezise the ion [Co(en)2(NO2)2]+. It
was the existence of two geometric isomers that provided crucial evidence on the structure of
coordination compounds. Draw (a) the two geometric isomers; (b) a linkage isomer of one of the
geometric isomers.
18.14 Deduce the probable formula of the simplest carbonyl compound of chromium. Show your
caculation.
18.15 Chromium forms two common anionic carbonyls: Cr(CO)5 n- and Cr(CO)4 m-. Deduce the
probable charges, n and m, on these ions.
18.16 Suggest why V(CO)6 is easily reduced to V(CO)6 - .
18.17 At very low temperatures, vanadium forms a compound with dinitrogcn, V(N2)n. Suggest
the value of x and give your reason.
18.18 Manganese forms a carbonyl of formula
Mn2(CO)10 with a structure of (OC)5Mn-Mn(C0)5. If the manganese atoms share one electron
each, does each manganese atom obey the 18 electron rule? Show your calculations.
18.19 Construct energy level diagrams for both hlgh and low spin situations for the d6 electron
configuration in (a) an octahedral field; (b) a tetrahedral field.
18.20 Which on of the iron(III) complexes, hexacyanoferrate(III) ion or tctrachloroferrate(III) is
likely to be high spin and which low spin? Give your reasons (two In each case).
18.21 The crystal field splittings, ∆, are listed below for three ammine complexes of cobalt.
Explam the differences in Values.
Complex ∆ (cm-1)
[Co(NH3)6 ]3+ 22 900
[Co(NH3)6 ]2+ 10 200
[Co(NH3)4 ]2- 5900
18.22 The crystal field splittings, ∆ are listed below for four complexes of chromium(III).
Explain the differences In values.
Complex ∆ (cm-1)
 [CrF6]3- 15 000
[Cr(OH2)6 ]3+ 17 400
[CrF6]2- 22 000
[Cr(CN)6 ]3- 26 600
18.23 Construct a table of d electron configurations and corresponding number of unpaired
electrons for a tetrahedral stereochemistry (similar to Table. 18.2).

18.24 Construct a table of crystal field stabilization energies for the dipositive high-spin ions of
the Period 4 transition metals in a tetrahedral field in terms of ∆ (similar to Table 18.3).
18.25 would you predict that in NiFe2O4 would adopt a normal spinel or an inverse spinel
structure? Explain your reasoning.
18.26 would you predict that in NiCr2O4 would adopt a normal spinel or an inverse spinel
structure? Explain your reasoning.
18.27 the compound, IrCl(CO)(PPh3)2, is known as vsaka’s compound and it is used for the
study of oxidative addition processes. What is the formal oxidation number of iridium in this
compound?
18.28 ortho-phenanthroline, C8H6N2, is a bidentate ligand, commonly abbreviated as phen.
Explain why [Fe(phen)3]2+ is paramagmetic.
18.29 the ligand, H2NCH2CH2NHCH2CH2NH2, commonly known as det , is a tridentate ligand,
coordinating to metal ions through all three nitrogen atoms. Write a balanced chemical equation
for the reaction of this ligand with th hexaaquanickel(II) ion and suggest why the formation of
this complex would be strongly favored.
BEYOND THE BASICS
18.30 Copper(l]) normally forms a complex chloro-anion of formula; [CuCl4]2- with cations such
as cesium. However, the cation [Co(NH3)6]3+ can be used to precipitate a chloro-anion of
formula [CuCl5]3- Suggest two reasons why this cation stabilizes the formation of the [CuCl5]3-
anion. Also, give the correct name for the complete compound formed.
10.31 Suggest why nickelocene, NI(C5H5)2, is readily oxidized. Give your reasoning.
18.32 A complex of nickel, Ni(PPh3)2Cl2 is paramagntic whereas the palladium analog,
Pd(PPh3)2Cl2, is diamagnetic. How many isomers would you predict for each compound? Gwe
your reasoning.
18.33 Iridium forms a compound [Ir(C5H5)(H3)(PPh3)]+. Two posible structures were proposed,
one containing three separate hydride ions and the other containing the unusual trihydrogen
ligand, H3.
(a) What would be the oxidation state of the iridium if the compound contained three hydride-
ions?
(b) If the compound contained a single H3 ligand, and the iridium had the same oxidaoon state as
that in Vaska’s compound (Exercise 18.27), what would be the charge on the H3 unit? By
comparison with diborane, suggest why this trihydrogen ion might indeed exist.
18.34 with the availability of many oxidation states, latimer, Frost, and Pourbaix diagrams are of
considerable importance in the study of transition metal chemistry, as we will see in Chapter 19.
For the imaginary transition metal, M, the Latimer diagrams is as follows:

(a) identify any species prone to disproportionation, and write the corresponding chemical
equation;
(b) calculate the the pH below which the reaction:

Becomes spontanecus. Assume standard conditions except for [H+(aq)].

18.35 which of the following ions will have the greater stability: [AuF2]- or [AuI2]-. Give your
reasoning.

18.36 nickel forms an anion [NiSe4]2- that is square planar while the analogous zinc anion,
[ZnSe4]2-, is tetrahedral. Suggest an explanation for the different stuctures.
18.37 iron(III) chloride reacts with triphenylphosphine, PPh3, to form the complex FeCl3(PPh3)2.
However, with the ligand tricyclohexylphosphine, PCh3, the compound FeCl3(PCh3) is formed.
Suggest a reason for the difference.
18.38 many tinned or bottled food products, such as commercial mayonaise, salad dressings, and
kidney beans, contain the hexadentate ligand ethylenediamminetetraacetate, 2-
(OOC)2NN(COO)22-, abbreviated edta4-, or a related compound. Suggest a reason for this.
18.39 three hydrates of chromium(III) chloride are known: form A is a hexahydrate; form B, a
pentahydrate; and form C, a tetrahydrate. Addition of excess silver ion solution to a solution of
one mole of each form results in the precipitation of the following number of moles of silver
chloride: form A-three; form B-two; form C-one. Form this information, deduce the actual
structure of each hydrate and write the correponding name