CHEM261: Applied inorganic chemistry

for chemical engineers

Part 1A: Transition Metal Chemistry

Prof. M.D. Bala

Room 3-64, Block H

Westville Campus

bala@ukzn.ac.za

Tel: ext. 2616

CHEM261 H1: 14L-0T-18P-0S-25H-20R-0F-0G-3A-13W-8C)

Prerequisites: CHEM161 and CHEM 171.

Module aim: To provide students with a basic understanding and relevant skills in selected
areas of Inorganic Chemistry.

Module structure
This course consists of different and quite diverse aspects of inorganic chemistry, which the
School of Engineering has asked the School Chemistry and Physics to cover. The main topics
are listed below. It should be noted that with such a diverse set of topics there will be no
perfect textbook to rely upon which encompasses all features of the module. Much of the
content is however present in any of the advance inorganic textbooks that are present in the
main library. Good books are Miesler & Tarr: Inorganic Chemistry (2nd or 3rd edn.,
Prentice Hall); Cotton, Wilkinson, Gaus: Basic Inorganic Chemistry (3rd edn, Wiley);
Shriver & Atkins: Inorganic Chemistry (4th edn., Oxford), Constable and Constable:
Inorganic Chemistry (Prentice Hall, but bad binding).
1. Transition metal chemistry
An introduction to metal complexes
Coordination number
Types of ligands.
Crystal field theory
2. Bonding
Simple bonding concepts.
Intermolecular bonding in selected systems.
3. Crystal structure
Simple crystal shapes. The radius ratio rule. Lattice energies, the Born-Haber cycle
and Madelung constant.
4. Transition metal processes
This will include discussions of the chemistry involved in the isolation and
purification of an important transition or non-transition metal - Cu.
Transition elements: Where are they on the periodic table?

The transition elements are also called the d block metals

General:

(a) Each group of d-block metals consists of three members called a

triad: e.g. Ti, Zr and Hf are members of the group 4 triad.

(b) Ru, Os, Rh, Ir, Pd and Pt are collectively called the platinum-
group metals.

(c) Important areas of study for the d-block elements:

i) electronic configuration
iii) (para)magnetism
iv) complex formation and coordination chemistry
Electron Configuration of Transition-Metal Ions:
The relationship between the electron configurations
of transition-metal elements and their ions is
complex.
Example: Let's consider the chemistry of cobalt
which forms complexes that contain either Co2+ or
Co3+ ions.
Co: [Ar] 4s2 3d7
Co2+: [Ar] 3d7
Co3+: [Ar] 3d6
In general, electrons are removed from the valence
shell s orbitals before they are removed from valence
d orbitals when transition metals are ionized.
Multiple Oxidation states
d-orbital occupation and electronic configurations:

To determine the electronic configuration of the central

metal ion in any complex
Recognise all the entities making up the complex and
knowing whether the ligands are neutral or anionic
So that you can determine the oxidation state of the
metal ion
A simple procedure exists for the M(II) case
22 23 24 25 26 27 28 29
Ti V Cr Mn Fe Co Ni Cu

Cross off the first 2,

2 3 4 5 6 7 8 9
Electronic configuration

(a) V is the third element in the 3d series, so its configuration is

[Ar]4s23d3. When it forms V3+, it loses the two 4s e- first, then one
of the 3d e-:
[Ar]3d2

Hence: V3+ is a d2 ion

(b) Mo lies below Cr in group 6B(6), so we expect the same exception

as for Cr. The configuration for Mo is therefore [Kr]5s14d5.
Formation of the Mo3+ ion occurs by loss of the single 5s electron
followed by two 4d electrons:

[Kr]4d3

Hence: Mo3+ is a d3 ion

Oxidation States and their Relative Stabilities:
Why do these elements exhibit a variety of oxidation states?
Because of the closeness of the 3d and 4s energy states.
Part 1B: Transition Metal Chemistry

Nomenclature - the systematic naming of

coordination compounds
 Ligands
The ligands of a complex ion are molecules or anions
with one or more donor atoms.
Each donor atom donates a lone pair of electrons to
the metal ion to form a covalent bond.

Ligands are classified in terms of their number of

donor atoms, or “teeth” ”:
- Monodentate ligands bond through a single donor
atom.
- Bidentate ligands have two donor atoms, each of
which bonds to the metal ion.
- Polydentate ligands have more than two donor
atoms.
Common ligands
 Coordination compounds

A coordination compound contains at least one complex ion, which

consists of a central metal cation bonded to molecules and/or anions
called ligands.

The complex ion is associated with counter ions of opposite charge.

The complex ion [Cr(NH3)6]3+ has a central Cr3+ ion bonded to six
NH3 ligands. The complex ion behaves like a polyatomic ion in
solution.
 Coordination compounds

The coordination number is the number of ligand atoms bonded directly

to the central metal ion.

Coordination number is specific for a given metal ion in a particular

oxidation state and compound.

- [Cr(NH3)6]3+ has a coordination number of 6.

The most common coordination number in complex ions is 6, but 2 and 4

are often seen.
 Geometry coordination compounds

The geometry of a given complex ion depends both on the

coordination number and the metal ion.

Coordination
Number Shape Examples

2 Linear [CuCl2]-, [Ag(NH3)2]+, [AuCl2]-

4 Square planar [Ni(CN)4]2-, [PdCl4]2-,

[Pt(NH3)4]2+, [Cu(NH3)4]2+

4 Tetrahedral [Cu(CN)4]3-, [Zn(NH3)4]2+,

[CdCl4]2-. [MnCl4]2-

6 Octahedral [Ti(H2O)6]3+, [V(CN)6]4-,

[Cr(NH3)4Cl2]+, [Mn((H2O6]2+,
[FeCl6]3-, [Co(en)3]3+
Coordination Numbers and Geometries:
 Nomenclature NaCl

Al(OH)2

How do we name such inorganic complexes? [Co(NH3)6]Cl3

Nomenclature is important in Coordination Chemistry

because of the need to have an unambiguous method of
describing formulae and writing systematic names,
particularly when dealing with isomers. Note however that
most textbooks do not use the latest IUPAC rules and in some
cases have made up their own rules and so can NOT be relied
on for guidance.
Rules:
1. In naming the entire complex, the name of the cation is
given first and the anion second (just as for NaCl =
sodium chloride), no matter whether the cation or the
anion is the complex species.
E.g. [Co(NH3)6]Cl3 = hexaamminecobalt(III) chloride
2. In the complex ion, the name of the ligand or ligands
precedes that of the central metal atom. (This procedure
is reversed from writing formulae)

[Co(NH3)6]Cl3 -hexaamminecobalt(III) chloride

K3 [Fe(CN)6] – potassium hexacyanoferrate(III)

3. Ligand names generally end with 'o' if the ligand is

negative ('chlorido' for Cl-, 'cyanido' for CN-, 'hydrido'
for H-) and unmodified if the ligand is neutral
('methanamine' for MeNH2)

Special ligand names are 'aqua' for water, 'ammine' for

ammonia, 'carbonyl' for CO, 'nitrosyl' for NO
4. A Greek prefix (mono, di, tri, tetra, penta, hexa, etc.)
indicates the number of each ligand (mono is usually
omitted for a single ligand of a given type). If the name
of the ligand itself contains the terms mono, di, tri, e.g.
triphenylphosphine, then the ligand name is enclosed in
parentheses and its number is given with the alternate
prefixes bis, tris, tetrakis instead.
For example, NiCl2(PPh3)2 is named
dichloridobis(triphenylphosphane)nickel(II)
5. Ligands are named in alphabetical order
use ligand name, not prefixes
example: [Co(NH3)4Cl2]+
amine first – starts with an a, even though we use
tetraammine chlorido second – starts with c, even
though we use dichlorido
Thus: tetraamminedichloridocobalt(III)
6.Two systems for showing charge or oxidation number

Stock system – calculated oxidation number of metal

roman numeral in parentheses after name of
coordination sphere
more common convention

Ewing-Basset – charge on coordination sphere in

parenthesis after name of coordination sphere

e.g [Pt(NH3)4]2+
tetraammineplatinum(II) or
tetraammineplatinum(2+)

N.B. If the charge is negative: add suffix –ate to name of

coordination sphere
7. The prefixes cis- and trans- designate adjacent
and opposite geometric locations

8. Bridging ligands between two metal ions have the

prefix µ-

9. When certain T.M. complexes are negatively

charged, the following metal names are employed

Fe iron ferrate
Ag silver argentate
Pb lead plumbate
Sn tin stannate
Sb antimony stilbate
Au gold aurate
Components of a coordination compound

• A coordination compound may consist of

– a complex cation with simple anionic counterions,
– a complex anion with simple cationic counterions, or
– a complex cation with complex anion as counterion.
• When writing the formula for a coordination compound
– the cation is written before the anion,
– the charge of the cation(s) is/are balanced by the charge of the
anion(s), and
– neutral ligands are written before anionic ligands, and the formula
of the whole complex ion is placed in square brackets.
Charge on the metal
The charge of the cation(s) is/are balanced by the charge of the
anion(s).

K2[Co(NH3)2Cl4] contains a complex anion.

The charge of the anion is balanced by the two K+ counter ions, so the
anion must be [Co(NH3)2Cl4]2-.

There are two neutral NH3 ligands and four Cl- ligands. To have an
overall charge of 2-, the metal ion must have a charge of 2+.
Charge of complex ion = charge of metal ion + total charge of ligands
2- = charge of metal ion + [(2 x 0) + (4 x -1)]
Charge of metal ion = (-2) – (-4) = +2 or 2+

The metal ion in this complex anion is Co2+.

[Co(NH3)4Cl2]Cl contains a complex cation.

The charge of the cation is balanced by the Cl- counter ion, so the
cation must be [Co(NH3)4Cl2]+.

There are four neutral NH3 ligands and two Cl- ligands. To have an
overall charge of 1+, the metal ion must have a charge of 3+.
Charge of complex ion = charge of metal ion + total charge of ligands
1+ = charge of metal ion + [(4 x 0) + (2 x 1-)]
Charge of metal ion = (+1) – (2-) = +3 or 3+

The metal ion in this complex cation is Co3+.

 Isomerism in coordination compounds
At the end of this section, you should be able to answer the following
questions:
1. What are isomers? = iso + mer = same (similar) + molecule (formula)
2. What are the important types of isomerism in coordination compounds?
3. Give examples of various compounds that show isomerism.
Constitutional isomers of coordination compounds.

Compounds with the same formula, but with the atoms connected
differently, are constitutional isomers.

Coordination isomers occur when the composition of the complex ion,

but not the compound, is different.
- This can occur by the exchange of a ligand and a counter ion, or be by
the exchange of ligands.

Linkage isomers occur when the composition of the complex ion is the
same but the ligand donor atom is different.
- Some ligands can bind to the metal through either of two donor atoms.
 Coordination isomers:
[Co(NH3)6]3+ and [Cr(CN)6]3- Vs: [Cr(NH3)6]3+ and [Co(CN)6]3-
[Co(NH3)6] [Cr(CN)6] [Cr(NH3)6] [Co(CN)6]

Linkage isomers:

e.g. Nitro and nitrito, N

or O coordination
possible
A pair of linkage (constitutional) isomers [Co(NH3)5NO2]2+

The nitrite ion can bind either through the N atom or either one of
the O atoms.
Stereo isomers

Stereoisomers are compounds that have the same atomic connections but
different spatial arrangements of their atoms.
Geometric or cis-trans isomers occur when atoms or groups can either
be arranged on the same side or on opposite sides of the compound
relative to the central metal ion.
Optical isomers (enantiomers) are non-superimposable mirror images of
each other.

The cis and trans isomers of [Pt(NH3)2Cl2].

In the cis isomer, identical ligands are adjacent to each other, while in the
trans isomer they are across from each other.
The cis isomer (cisplatin) is an antitumor agent while the trans isomer
has no antitumor effect.
Geometric (cis-trans) isomerism.

The cis and trans isomers of [Co(NH3)4Cl2]+.

Note the placement of the Cl- ligands (green spheres).

In the cis isomer, the angle between the two Cl- ions = 90°
°

In the trans isomer the angle between the two Cl- ligands = 180°
°
 Optical isomerism in an octahedral complex ion

Structure I and its mirror image, structure II, are optical isomers
of cis-[Co(en)2Cl2]+.
 Optical isomerism in an octahedral complex ion

The trans isomer of [Co(en)2Cl2]+ does not have optical isomers.

Structure I can be superimposed on its mirror image, structure II.