INTENDED LEARNING OUTCOME

➢ Describe the general properties of

transition metals

➢ Name and write the formula of

coordination compounds; predict the
type of isomerism of coordination
compounds
Transition Elements
➢Elements or metals found
in the middle of the periodic
table
➢Large block of elements
occupies the central portion
of the periodic table
 TRANSITION ELEMENTS: coined to
denote transition between the “base
formers” on the left (Na, Ca) and the
“acid formers” on the right (C, N, S,
Cl)
▪ Typically have incompletely filled
d subshells or readily give rise to
ions with incompletely filled d
subshells (except Zn, Cd, and Hg)
Transition Elements
Similarity of elements within the
row is stronger than within the
group
Attributed to the fact that going
across the row, electrons are not
added to an outer shell but instead
to the d and f subshell of an inner
shell.
 Types of Transition Elements
Transition elements are divided
into 2 types depending on the
valence electrons involved:
1st type: the d-block elements noted
for their occurrence that coincides
with the filling of the d orbitals.
 Types of Transition Elements
2nd type: the f-block elements
characterized by the filling of the f
orbitals
Contained in the f-block elements
are 2 sub-groups namely the
lanthanides and the actinides
elements
General Properties
 All are metals
 Most are harder, more brittle, have higher
MPs, BPs and ΔHvap than nontransition metals
 Ions and compounds are usually colored
 They exhibit multiple oxidation states
 Many, including they compounds, are
paramagnetic
 Many of the metals and their compounds are
catalysts
 Other Properties of Transition Elements
(1) Solids at normal condition (with the exception
of Hg)
(2) Conductor of electricity
(3) React with various oxidizing agents yielding
ionic compounds
(there is a considerable variation in the reaction
especially for silver, gold and platinum which are
resistant to oxidation and tarnishing)
(4) High melting and boiling points (except Hg)
✓Oxidation States of the First Row Transition
Metals
 Transition Metal Compounds
 Cobalt is a crucial element in vitamin B12.
 Iron is contained in hemoglobin and myglobin.
 Many are highly colored making them useful as
dyes and pigments (Prussian blue contains iron
while white paints contains titanium)
 Transition Metal Compounds
 Presence of transition metal ions in
crystalline silicates and alumina forms
gemstone (iron causes yellow color of
citrine while chromium the red color in
rubies).
 Colored glasses contain transition metal
(blue glass contains cobalt while green
glass has chromium)
 Solutions of compounds of
transition metal complexes

✓[Fe(H2O)6] ✓[Ni(H2O)6]2 ✓[Zn(H2O)6]

3+ + 2+
✓[Co(H2O)6] ✓[Cu(H2O)6]2
2+ +
 Compounds of
transition metal complexes

✓http://genchem.chem.wisc.edu/demonstrations/Gen_Chem_Pages/20transmetalpage/colors_of_complexes_of_tra.htm
Transition Metal Gems
 Gemstones owe their color from trace transition-
metal ions
Examples:
Corundum mineral, Al2O3: Colorless

✓Ruby: Cr ✓Amethyst: Mn ✓Sapphire: Ti &

Co
 Gemstones owe their color from trace transition-
metal ions
Examples:
Beryl, Be3 Al2Si6O18 : Colorless

✓Aquamarine: Fe
✓Emerald: Cr, V
 Reaction with oxygen
The transition metals react with oxygen
at normal conditions forming their
corresponding oxides:
Ti + O2 → TiO2
Mx + ½ O2 → MxO
2 My + 3/2 O2 → My2O3

Mx represents Ni, Cu and Zn

My represents Sc, Cr and Fe
 Reaction with oxygen
The transition metals react with oxygen
at normal conditions forming their
corresponding oxides:

2 V + 5/2 O2 → V2O5
3 Mz + 2 O2 → Mz3O4

Mz represents Mn and Co
 Reaction with chlorine
The transition metals react with
chlorine forming chlorides:
Mx + Cl2 → MxCl2
My + 3/2 Cl2 → MyCl3
Mz + 2 Cl2 → MzCl4
Mx represents Mn, Co, Ni, Cu and Zn
My represents Sc, Cr and Fe
Mz represents Ti and V
 Reaction with HCl(aq)
The transition metals react with
hydrochloric acid forming cations:
Mx → Mx2+(aq)
My → My3+(aq)
Mx represents Cr, Mn, Fe, Co, Ni, and Zn
My represents Sc and Ti
V and Cu have no reaction
 Application
✓ Nitinol – “memory metal”, a name
constructed out of its composition
metal which is Ni and Ti.
✓ Nitinol was first intended for used
in missile cones but instead found
its way in medicine as fabricated
vascular stents, surgical anchors,
dental braces in orthodontics and
even in sunglasses.
Memory Metal
Memory metal is an alloy with
about the same number of Ni and
Ti atoms. When the alloy is in a
highly symmetric shape (austenite)
it is rigid and can be twisted, bent
or mold to the desired shape.
 Memory Metal
When the alloy is cooled below
its phase transition temperature, it
enters a less symmetric but flexible
phase (martensite). The alloy
becomes soft and may be twisted or
bent out of shape. When warmed, it
returns to its original shape.
Definitions
 Coordination compound
- any compound that contains a coordination entity;
compounds containing complexes

 Coordination entity
- an ion or neutral molecule that is composed of a
central metal to which is attached an array of other
atoms or groups of atoms.
In formulae, the coordination entity is enclosed by
square brackets whether charged or uncharged.
Metal Complex
•Central metal atom bonded to a group
of molecules or ions

•Complex Ion
•Charged metal complexes
Examples of Coordination Entities
 [CoCl(NH3)5]2+
 [PtCl4]2-

 [Fe3(CO)12]
Definitions
 Central atom: atom in the CE which binds other
atoms or groups of atoms
 Ligands: atoms or groups of atoms bound to the
central atom
 Coordination polyhedron: The ligand atoms directly
attached to the central atom define a coordination
polyhedron about the central atom.
Definitions
 Coordination number: number of σ-bonds between
ligands and the central atom; usually equal to the
number of vertices in the coordination polyhedron
Coordination number – no. of ligands attached
to the metal ion
Co(H2O)62+ 6
CoCl42- 4
Cu(NH3)42+ 4
Ag(NH3)2+ 2
 Metal complexes have characteristic shapes,
depending on the metal ion’s coordination number.
 Two-coordinate complexes are linear.
 (eg. [Ag(NH3)2] +)
 Four-coordinate complexes are either tetrahedral or
square planar; for example, [Zn(NH3)4] +2 is
tetrahedral, and [Ni(CN)42-] is square planar.

 Nearly all six-coordinate complexes are octahedral

Definitions
 Oxidation state: The oxidation state of the metal is
defined as the charge it would have if all ligands are
removed along with the electron pairs that were
shared with the central atom.
 It is represented by a Roman numeral.
Example 1
 A cobalt(III) ion forms a complex with four ammonia
molecules and two chloride ions. What is the formula
of the complex?
 Solution:
Example 2
 What is the oxidation state of platinum in the
coordination compound K[Pt(NH3)Cl5]?
 Solution:
Examples of Coordination Compound
 [CoCl(NH3)5]Cl2
Determining Oxidation States and
Coordination Numbers
 [CoCl(NH3)5]Cl2

 K [Cr(NCS)4(NH3)2]

 [Cr(NH3)6][CuCl5]
Ligands
 Because all ligands are Lewis bases, they have at least
one lone pair of electrons that can be used to form a
coordinate covalent bond to a metal ion.

 They can be classified as monodentate or polydentate,

depending on the number of ligand donor atoms that
bond to the metal.
Monodentate Ligands
 using the electron pair of a single donor atom for
bonding.
Polydentate Ligands
 Those that bond through electron pairs on more than
one donor atom are termed polydentate ligands
(“many-toothed” ligands).
 They are known as chelating agents (from the Greek
word chele, meaning “claw”) because their multipoint
attachment to a metal ion resembles the grasping of an
object by the claws of a crab
Definitions
 Chelation: simultaneous coordination of more than
one-electron pair donor from the same ligand to the
same central atom

 Denticity: number of donor atoms from a given ligand

simultaneously attached to the same central atom
 ✓bidentate
chelation

✓tetradentat
e chelation

✓tridentate
chelation

✓The number of ligating atoms in a chelating ligand

is indicated by: bidentate, tridentate, tetradentate, etc
Chelates
 The cyclic structures formed when more than one
donor atom from the same ligand is bound to the
central atom
Some Common Chelating Ligands
 ethylenediamine (en)

• diethylenetriamine(dien)
Some Common Chelating Ligands
 triethylenetetraamine (trien)
✓Hexadentate: ethylenediaminetetraacetate ion
(edta)
Describing Coordination Compounds
 Write names
 Write formulae
 Draw structures
Naming Coordination Compounds
 In the early days of coordination chemistry,
coordination compounds were named after their
discoverer or according to their color.
Naming Coordination Entities
IUPAC Rules
1. When writing the name of a complex:
the positive ion is named first followed by the negative
ion, with a space in between the names.

Ligand names are listed before the name of the central

atom

Formula: K3[Fe(CN)6 ]

Name: Potassium hexacyanoferrate(III)

Naming Coordination Entities
IUPAC Rules
2. No spaces are left between parts of the name that refer to
the same coordination entity

Formula: [Cr(H2O)4Cl2]Cl
Name: tetraaquadichlorochromium(III) chloride.

*The name of a complex is one word, with no

space between the various ligand names and
no space between the names of the last ligand
and the metal.
Naming Coordination Entities
IUPAC Rules
3. Ligand names are listed in alphabetical order,
regardless of the charge of the ligand

Formula: [Cr(H2O)4Cl2]Cl
Name: tetraaquadichlorochromium(III) chloride
Naming Coordination Compounds
4. To indicate number of ligands of one kind in a
coordination entity two kinds of prefixes may be used:
a. Di, tri, etc., are used for simple ligands.
( ) not required.

Formula: [Cr(H2O)4Cl2]Cl
Name: tetraaquadichlorochromium(III)
chloride
Naming Coordination Compounds
4. To indicate number of ligands of one kind in a
coordination entity two kinds of prefixes may be
used:
b. Bis, tris, tetrakis, etc. are used with complex
expressions and to avoid ambiguity ( ) must be
placed around ligand name
Ex: [PtCl2(NH2Me)2]
dichlorobis(methylamine)platinum(II)
Numerical prefixes
1 mono
2 di (bis)
3 tri (tris)
4 tetra (tetrakis)
5 penta (pentakis)
6 hexa (hexakis)
7 hepta (heptakis)
8 octa (octakis)
9 nona (nonakis)
 10 deca (decakis)
Naming Coordination Compounds
5. Representing ligands in names:
a. Names of anionic ligands are modified to end in
“o”.
In general:
“ide” → “ido”
“ite” → “ito”
“ate” → “ato”
Examples of anionic ligands
- fluoro - cyano
F CN
(fluorido) (cyanido)

H- hydrido CH3COO- acetato

OH - hydroxo HS - mercapto

O2 2- peroxo S2- thio

CO3 2- carbonato C2O4 2- oxalato

Naming Coordination Compounds
5. Representing ligands in names:
b. Names of neutral and cationic ligand names
are used without modification
Some common ligands have special names:

H2O aqua NO nitrosyl

NH3 ammine O2 dioxygen

CO carbonyl N2 dinitrogen
Naming Coordination Compounds
5. Representing ligands in names:
c. Enclosing marks are needed for neutral and
cationic ligands, for inorganic ligands
containing numerical prefixes, for any
compositional name, for any substituted
organic ligand and whenever necessary to
avoid ambiguity.
d. However, common ligands such as aqua,
ammine, carbonyl, nitrosyl, methyl, ethyl,
etc., do not require enclosing marks, unless
there is ambiguity.
Naming Coordination Compounds
6. All anionic coordination entities take the ending
'ate', whereas no distinguishing termination is used
for cationic or neutral coordination entities.
Ex:
Potassium hexacyanoferrate(III)
Pentaamminechlorocobalt(III) nitrate
dichlorobis(methylamine)platinum(II)
✓Names of Some Metallate Anions
Naming Coordination Compounds
7. Charge numbers, oxidation numbers, and ionic
proportions:
a. Oxidation numbers (STOCK system; more
common; recommended by IUPAC)
i. The oxidation number of the central atom is
indicated by a Roman numeral enclosed in
parenthesis after the name of the central
atom name.
Arabic zero indicates the zero oxidation
number.
Naming Coordination Compounds
7. Charge numbers, oxidation numbers, and ionic
proportions:
a.Oxidation numbers
ii. Alternatively, the charge on a coordination
entity may be indicated:
The net charge is written in arabic numbers,
with the number preceding the charge sign,
and enclosed in parentheses (EWING-
BASSET system).
It follows the name of the central atom
without the intervention of a space.
Zn (OH)4-
Stock: _____________________
Ewing Bassett:_______________

[Cr(H2O)4Cl2]Cl
Stock: _____________________
Ewing Bassett:_______________
Naming Coordination Compounds
7. Charge numbers, oxidation numbers, and ionic
proportions:
b. The proportions of ionic entities may be given by
using stoichiometric prefixes on both ions.
 Name the following:
[Cr(H2O)3(NH3)2(OH)](NO3)2
✓List the name and charge of each ligand:
✓ H2 O
✓ NH3
✓ OH-
✓Determine oxidation state of metal:
✓Cr(III)
✓ Name:
diamminetriaquahydroxochromium(III)
nitrate
Examples
Formula: K2[Cr(CN)2NH3(O2)O2]

Name: Potassium
amminedicyanodioxoperoxochromate(VI)
Name the following:
K[PtCl3(C2H4)]

✓Potassium trichloro(ethylene)platinate(II)
Name the following:
[NiCl2 (en)2]

✓Dichlorobis(ethylenediamine)nickel(II)
Name the following:
[Co(NH3)6]Cl3

✓hexaamminecobalt(III) chloride
Name the following:
[Rh(NH3)5I]I2

✓pentaammineiodorhodium(III) iodide
Name the following:
Fe(CO)5

✓pentacarbonyliron(0)
Name the following:
Na3[Fe(CN)6] · 2H2O

✓sodium hexacyanoferrate(III)
dihydrate
Formulae of Coordination Compounds
1. Sequence of symbols within the coordination entity
formula
a. The central atom is listed first.
b. The ligands are then listed in alphabetical order
according to the first symbol of the ligand
formula or ligand abbreviation as written.
Example: hexaaquacobalt(II) sulfate
Formula:[Co(H2O)6]SO4
Formulae of Coordination Compounds
2. Use of enclosing marks
a. The formula for the entire coordination entity,
whether charged or not, is enclosed in square
brackets.

Example: bis(ethylenediamine)platinum(II)
perchlorate
Formula: [Pt(en)2][ClO4]2
Formulae of Coordination Compounds
2. Use of enclosing marks
b. When ligands are polyatomic, their formulae are
enclosed in parentheses. Ligand abbreviations are
also usually enclosed in parentheses.
Example: hexaaquacobalt(II) sulfate
Formula: [Co(H2O)6]SO4
 ✓Examples
✓In the lab:
 [PtBrCl(NH3)(NO2)] - WRITING
 [PtCl2(NH3)(py)] FORMULAE: Ligands
are listed in the ff.
 [Co(en)F2(NH3)2]+ order: negative ions,
neutral molecules,
 [Co(NH3)5(N3)] 2+ positive ions. Ligands
with the same charge
are listed in
 Amminebromochloronitroplatinate(II) alphabetical order.
 Amminedichloro(pyridine)platinum(II)
 Diammine(ethylenediamine)difluorocobalt(III)
 Pentaammineazidocobaltate(III)
1st Row Transition Metals