Professional Documents
Culture Documents
Coordination Compounds
CHM361: Inorganic Chemistry
Topic Outline
Transition Metals
Coordination Compounds
Isomerism
Bonding in Complex Ions
Transition Metals
Transition Metals
Transition
metals
typically have
incompletely
filled d
subshells or
readily give
rise to ions
with
incompletely
filled d
subshells
+2
Mn2+
+6
MnO4
+7
MnO4
Coordination Compounds
A coordination compound (or
complexes) typically consists of a complex
ion and a counter ion
A complex ion contains a central metal
cation bonded to one or more molecules or
ions, called ligands
A ligand has at least one unshared pair of
valence electrons
Coordination Compounds
H
Examples of ligands
Cl
Coordination Compounds
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
Coordination Compounds
The atom in a ligand that is bound directly to
the metal atom is the donor atom
Coordination Compounds
Coordination Compounds
Bidentate and
polydentate ligands are
called chelating agents
[Co(en)3]2+
[PbEDTA]2-
Coordination Compounds
Coordination Number
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
The most common coordination number in
complex ions is 6, but 2 and 4 are often seen
Coordination Compounds
Oxidation Number
The net charge of a complex ion is the sum
of charges on the central metal & its ligands
In [Pt(Cl)6]2-, the oxidation number of Cl is -1,
therefore for Pt = -2 + 6(1) = +4
If the ligands have no charge, then the
oxidation number for the metal is the same
as the charge of the complex ion, such as in
[Cu(NH3)4]2+, where the oxidation number of
Cu is +2
Name
Formula
Aqua
H2O
Ammine
NH3
Carbonyl
CO
Nitrosyl
NO
Formula
Fluoro
F-
Chloro
Cl-
Bromo
Br-
Iodo
I-
Nitro
NO2-
Nitrato
NO3-
Carbonato
CO32-
Acetato
CH3COO-
Hydroxo
OH-
Cyano
Formula
Aluminium
Aluminate
Chromium
Chromate
Cobalt
Cobaltate
Copper
Cuprate
Gold
Aurate
Iron
Ferrate
Lead
Plumbate
Nickel
Nickelate
Silver
Argentate
Tin
Stannate
Zinc
Zincate
Metals in Complex Anions
Exercises
Name the following compounds:
[Cr(NH3)3]Cl3
[Pt(en)]Cl2
K2[Cu(C2O4)Br2]
NH4[Fe(OH)4]
Exercises
Write the formula for the following
compounds:
Hexacarbonylmanganese(I) perchlorate
Tris(ethylenediamine)copper(II) sulfate
Potassium diaquatetracyanocobaltate(III)
Coordination No = 2
Coordination No = 4
Coordination No = 6
Isomerism
Isomers are compounds with the same
chemical formula but different in chemical
properties
The two main types of isomers in
coordination compounds are:
Structural/constitutional isomers: where atoms
are connected differently
Stereoisomers: where the arrangement in
space is different
Coordination isomers
Ionisation isomers
Hydrate isomers
Linkage isomers
Isomerism Structural
Isomers
Linkage isomers the composition of
complex ion is the same, but the ligand
donor atom is different, ie.
Isomerism - Stereoisomers
Geometric isomers (also called cis-trans
isomers or diastereomers) atoms/group of
atoms arrange differently in space relative to
the central ion
Isomerism - Stereoisomers
Optical isomers (also called enantiomers)
when a molecule and its mirror image cannot
be superimposed
Optical isomers are physically identical,
except for the direction they rotate polarised
light
A way to determine optical isomerism is by
rotating one molecule on its vertical axis to
see whether it can be superimposed on the
other
Isomerism - Stereoisomers
Isomerism - Stereoisomers
Isomerism - Stereoisomers
Example:
Isomerism - Stereoisomers
The square planar Pt(II) complex has two different
types of monodentate ligands. Each pair of
ligands can be next to each other or across from
each other. Thus geometric isomerism occurs.
They do not have optical isomers since each
compound is superimposable on its mirror image.
Isomerism - Stereoisomers
Ethylenediamine (en) is a
bidentate ligand. The Cr3+
ion has a coordination
number of 6 and an
octahedral geometry. The
three bidentate ligands
are identical, so there is
no geometric isomerism.
However, the complex
ion has a
nonsuperimposable
mirror image. Thus
optical isomerism
occurs.
Geometry
Example
sp
Linear
[Ag(NH3)2]+
sp3
Tetrahedral
[COCl4]2-
dsp2
Square
planar
[Ni(CN)4]2-
d2sp3 or
sp3d2
Octahedral
[Cr(H2O)6]3+
,
[Co(H2O)6]2
Different ligands
create crystal field of
differing strengths:
Strong field ligands:
larger splitting energy
Weak field ligands:
smaller splitting
energy
[V(H2O)6]
[V(H2O)6]
2+
3+
A change in oxidation
state causes a change in
color.
[Cr(NH3)6]
[Cr(NH3)5Cl ]
3+
2+
Substitution of an NH3
ligand with a Cl- ligand
affects the color of the
complex ion.
I- < Cl- < F- < OH- < H2O < SCN- < NH3 < en < NO2- <
CN- < CO
WEAKER
FIELD
SMALLER
LONGER
STRONGER
FIELD
LARGER
SHORTER
low spin:
strongfield
ligand
high spin:
weak-field
ligand
low spin:
strongfield
ligand