Transition Metal

Complexes I
The structures, nomenclature
and isomers of coordination
compounds

Coordination Compounds
Any compound containing a metal
atom or ion with one or more ligands
is called a coordination compound or
complex. The ligands donate
electrons to the metal via coordinate
covalent bonds.

Coordination Compounds
The structures of these compounds was
not always evident. Ions or molecules
might be directly bonded to the metal, or
serve as a counter ion for an ionic salt.
[Mn(OH2)6] SO4 sulfate ion is outer sphere
[Mn(OH2)5 SO4].H2O sulfate ion is inner
sphere

Coordination
Compounds
Early chemists approached transition
metal complexes using the concept of
valences adapted from main group
metals. Metals with a +3 charge, such as
iron(III) or cobalt(III) were believed to
only make three bonds.
A compound such as [Co(NH3)6]Cl3 was
thought to have three Co-Cl bonds, with
no way to explain the bonding of ammonia
in the compound.

Coordination Compounds
One approach by Blomstrand proposed
chains of linked ammonia molecules,
with the nitrogens having five bonds
and connecting a chloride to the metal.
Alfred Werner proposed that the
ammonia molecules could bond
strongly and directly to the metal, with
chlorides either directly bonded, or
loosely bonded and ionic in solution.

Coordination Compounds

Coordination Compounds
Jorgensen supported
Blomstrands approach, and Werner,
in order to support his theory,
synthesized new compounds and
studied their isomers. Eventually, in
1907, Werner prevailed and proved
the octahedral geometry of
coordination compounds.

Coordination Compounds
Alfred Werner (1866-1919) also
determined the formulas and
structures of many transition metal
compounds by studying their
isomers. Due to the existence of a
variety of structural isomers, he
proposed that complexes must have
square planar and octahedral
shapes.

Possible Structures for 6Coordinate Cobalt

Possible Structures for 6Coordinate Cobalt

Possible Structures for 6Coordinate Cobalt

Proposed Structures for

6-Coordinate Cobalt

Structure of Compounds
Composition # ions
formulation

Modern

PtCl2.4NH3

3 [Pt(NH3)4]2+ 2Cl-

PtCl2.3NH3

2 [PtCl(NH3)3]+Cl-

PtCl2.2NH3
(2 forms)

0 [PtCl2 (NH3)2]

Nomenclature of
Coordination Compounds
There is a separate system for naming
coordination compounds:
prefix indicating + ligand name + metal +
(oxidation #
# of ligands
in roman
numerals)
or

+ + + (charge of

complex)

Nomenclature of
Coordination Compounds
1. If ionic, the positive ion is named
first, then the negative ion.
2. The inner coordination sphere is
indicated by square brackets. In the
formula, the metal is written first,
followed by the ligands. In naming,
the ligands are named first, then the
metal.

Nomenclature of
Coordination Compounds
3. Prefixes: If the ligand itself contains a prefix
in its name (ex. dimethyl amine), then the
prefix to indicate the number of ligands
changes, and the ligand name is placed in
parenthesis.
2 di or bis 5 penta or pentakis 8 octa or octakis
3 tri or tris 6 hexa or hexakis
9 nona or nonakis
4 tetra or tetrakis
7 hepta or heptakis 10 deca
or decakis

Nomenclature of
Coordination Compounds
4. Ligands are listed in alphabetical order
(ignoring any prefixes). Most ligands have
special names, with all negatively charged
ligands ending in the lettero.
Most neutral ligands retain their usual
names, with the following common
exceptions:
NH3 ammine H2O aqua

CO carbonyl

Names of Common
Ligands
Formula Name
Brbromo
CO32- carbonato
Cl- chloro
CNcyano
H- hydrido
OHhydroxo
O2-oxo

Linkage Isomerism
Formula
NO2-

Name
nitrito (via O)

NO2-

nitro (via N)

Linkage Isomers
Linkage isomers
involve ligands that
may bond via different
sites. In this example,
nitro bonds via
nitrogen
(NO2-), and nitrito
bonds via an oxygen
(NO2-). The
compounds have
different properties
and colors.

Polydentate Ligands
Formula
NH2CH2CH2NH2
(en)

Name
ethylenediamine

Both amines of the

ligand can attach
at the metal
forming a ring.

Polydentate Ligands
ethylenediaminetetraacetate
(EDTA) EDTA is a hexadentate
ligand.

EDTA
EDTA can wrap
around a metal ion
to coordinate at 6
(octahedral) sites.
Ligands that bind
to more than one
site are called
chelating agents.

Nomenclature of
Coordination Compounds
5.
There are two systems for indicating the
oxidation number of the metal. The more
commonly used system indicates the oxidation
number in Roman numerals in parentheses after
the name of the metal.
The other system puts the charge of the
coordination complex in Arabic numbers in
parentheses after the metal.
[Cr(H2O)5Cl]2+ is pentaaquachlorochromium(III)
or, pentaaquachlorochromium(2+).

Nomenclature of
Coordination Compounds
6. Using either system, if the transition metal
complex is negative in charge, the name of
the metal ends in ate.
For example, [Pt(NH3)2Cl4]2- is named
diamminetetrachloroplatinate(II).
For metals with Latin names, the negatively
charge complex uses:
ferrate (for Fe)
argentate (for Ag)
plumbate (for Pb) stannate (for Sn)
aurate (for Au)
cuprate (for Cu)

Nomenclature of
Coordination Compounds
7. The complete name of the complex must
also indicate the presence of geometric
isomers. Prefixes such as cis, trans, mer,
and fac are used to indicate the relative
positions of similar ligands.
In addition, stereoisomers are also
possible with tetrahedral and octahedral
geometries, and optical isomers are
indicated with the prefixes and .

Nomenclature of
Coordination Compounds
8. Bridging ligands between two metal
atoms have the prefix .

Isomerism

Stereoisomerism
Stereoisomers have the same
connectivities but different spatial
arrangements.
In geometric isomers, the ligands have
different spatial arrangements about
the metal ion.
Optical isomers are compounds with
non-superimposable mirror images.

Geometric Isomerism
Geometric isomers differ in the geometric
arrangement of the ligands around the
central metal.
Common examples are square planar
complexes such as [Pt(NH3)2Cl2].

Geometric Isomerism
In octahedral complexes, the prefixes
cis and trans are used for complexes of
the form [MX4Y2]

Octahedral Complexes
For complexes with the formula
[MX3Y3], there are two spatial
arrangements of the ligands.

Octahedral Complexes
fac stands for facial, and mer
stands for meridian.

Chirality
Both four-coordinate and six-coordinate
complexes exhibit chirality. Chiral
molecules have either no symmetry
elements (other than identity), or only a
Cn axis.
Tetrahedral complexes can be chiral in
the same way that organic compounds
are: they may have four different ligands.
They may also have unsymmetrical
chelating ligands.

Chirality
Square-planar
complexes
can also be
chiral, as
seen in these
compounds of
platinum(II)
and
palladium(II).

Optical Isomers
Octahedral complexes containing
polydentate ligands can form optical
isomers. Complexes with three
rings, such as [Co(en)3]3+, can be
viewed like a propeller with three
blades. The structure can be either
left or right handed, with nonsuperimposable mirror images.

Optical
Isomers
The upper
isomer is right
handed, and the
lower one is left
handed.

Optical
Isomers

Optical
Isomers

Optical
Isomers

Optical
Isomers

Optical
Isomers

Optical Isomers
The righthanded isomer
requires going
clockwise to get
from the upper
triangle to the
lower one. The
prefix for this
isomer is .

Optical Isomers
The left-handed
isomer requires
going
counterclockwise
to get from the
upper triangle to
the lower one. The
prefix for this
isomer is .

Optical Isomers
Octahedral complexes with two
chelating ligands and two nonchelating ligands can also be
optically active.

Isomers

Co(III) and ethylenediamine react to

form several products.
cis[CoCl2(en)2]+ is violet, and the
trans isomer is green. The reaction
also forms a yellow product,
[Co(en)3]3+. Determine the number
of isomers of each of the products.
Label any enantiomers with the
proper prefix ( or ).

Isomer Problem
The yellow product is [Co(en)3]+3.
It exists as an enantiomeric pair.

Isomer Problem

The violet product consists of a pair of

optical isomers. The green product is not
optically active, as it has a mirror plane.

Common Coordination
Numbers & Structures

Factors Affecting
Coordination Number
1. The size of the central atom or ion.
2. Steric interactions between bulky
ligands such as P(C6H5)3.
3. The electronic structure of the metal
atom or ion. If the oxidation number is
high, the metal can accept more
electrons from the (Lewis base)
ligands. Metals with many d electrons
will have lower coordination numbers.

Coordination Numbers
Coordination numbers of 1, 2 and
3 are relatively rare. Coordination
number 4 leads to two common
structures: tetrahedral or square
planar geometry. Square planar
structures are most commonly seen
with d8 metals such as Ni(II), Pd(II)
or Pt(II), or when the ligand is
planar.

5 Coordinate Complexes
5 coordinate complexes with
monodentate ligands are often
highly fluxional, so that axial and
equatorial positions interchange.
Once such method of interchange of
these positions is via a Berry
pseudorotation.

Berry Pseudorotation
A

A
A

5 Coordinate Complexes
A planar
polydentate
ligand, such as a
porphyrin, may
result in square
pyramidal
structures, when a
fifth ligand is
added, such as in
myoglobin.

6-Coordinate Complexes
6-coordinate
complexes are
usually octahedral.
Sometimes
distortion from
octahedral
geometry occurs if
a bidentate ligand
has a small bite
angle.

6-Coordinate Complexes
In extreme
cases, the
staggered
configuration of
the octahedron
can be distorted
into a trigonal
prism.

7- Coordinate Complexes
These are
more
common for
f-block
elements,
and include
pentagonal
bipyramids,
capped
octahedrons
and capped
trigonal
prisms.