Coordination Chemistry I:

Structures and Isomers

Chapter 9

Coordination Compounds
Coordination compounds
compounds composed of a
metal atom or ion and one
or more ligands.
[Co(Co(NH3)4(OH2)3]Br6
Ligands usually donate
electrons to the metal
Includes organometallic
compounds

Werners totally inorganic

optically active compound.

Werners Coordination Chemistry

Performed systematic studies to understand bonding in
coordination compounds.
Organic bonding theory and simple ideas of ionic charges
were not sufficient.

Two types of bonding

Primary positive charge of the metal ion is balanced by
negative ions in the compound.
Secondary molecules or ion (ligands) are attached directly to
the metal ion.
Coordination sphere or complex ion.
Look at complex on previous slide (primary and secondary)

Werners Coordination Chemistry

He largely studied compounds with four or six
ligands.
Octahedral and square-planar complexes.

It was illustrated that a theory needed to account

for bonds between ligands and the metal.
The number of bonds was commonly more than
accepted at that time.
18-electron rule.

New theories arose to describe bonding.

Valence bond, crystal field, and ligand field.

Chelating Ligands
Chelating ligands
trisoxalatochromate(III) ion or just [Cr(ox) ]
(chelates) ligands that
have two or more points
of attachment to the
metal atom or ion.
3

Bidentate, tridentate,
tetra.., penta, hexa
(EDTA).

3-

A Hexadentate Ligand, EDTA

There are six points of
attachment to the calcium
metal.
Octahedral-type geometry
ethylene diamine tetraacetic acid
(EDTA)

ethylenediaminetetraacetatocalcium ion or just [Ca(EDTA)]2-

Nomenclature
The positive ion (cation) comes first, followed by the name
within the coordination sphere, followed by the negative ion
(anion).
These ions are not in the coordination sphere.
Diamminesilver(I)chloride and potassium hexacyanoferrate (III).

The inner coordination sphere is enclosed in brackets in the

formula. Within this sphere, the ligands are named before
the metal, but in formulas the metal ion is written first.
Tetraamminecopper(II) sulfate and hexaamminecobalt(III) chloride.

Nomenclature
The number of ligands is
given by the following
prefixes. If the ligand
name includes prefixes
or is complicated, it is
set off in parentheses
and the second set of
prefixes is used.
[Co(en)2Cl2]+ and
[Fe(C5H4N-C5H4N)3]2+

2
3
4
5
6
7
8

di
tri
tetra
penta
hexa
hepta
octa

bis
tris
tetrakis
pentakis
hexakis
heptakis
octakis

Nomenclature
Ligands are named in alphabetical order
(name of ligand, not prefix)
[Co(NH3)4Cl2]+ and [Pt(NH3)BrCl(CH3NH2)]+2

Anionic ligands are given an o suffix.

Neutral ligands retain the usual name.
Coordianted water is called aqua.
Chloro, Cl Sulfato, SO42-

Nomenclature
The calculated oxidation number of the metal ion is
placed as a Roman numeral in parentheses after the
name of the coordination sphere.
[Pt(NH3)4]+2 and [Pt(Cl)4]-2
A suffix ate is added to the metal ion if the charge is
negative.

The prefixes cis- and trans- designate adjacent and

opposite geometric location, respectively.
trans-diamminedichloroplatinum(III) and cistetraamminedichlorocobalt(III)

Nomenclature
Bridging ligands between two metal ions
have the prefix .
-amido--hydroxobis(tetraamminecobalt)(IV)

There is an error in this picture. What is it?

Isomerism
Our discussion of isomers will be largely
limited to those with the same ligands arranged
in different geometries. This is referred to as
stereoisomers.

Isomerism
Four-coordinate complexes
Square-planar complexes may have
cis and trans isomers. No chiral
isomers (enantiomers) are possible
when the molecule has a mirror
plane.
cis- and transdiamminedichloroplatinum(II)
How about tetrahedral complexes?
Chelate rings commonly impose a
cis structure. Why

Chirality
Mirror images are nonsuperimposable.
A molecule can be chiral if it has no rotation-reflection
axes (Sn)
Chiral molecules have no symmetry elements or only
have an axes of proper rotation (Cn).
CBrClFI, Tetrahedral molecule (different ligands)
Octahedral molecules with bidentate or higher chelating
ligands
Octahedral species with [Ma2b2c2], [Mabc2d2], [Mabcd3],
[Mabcde2], or [Mabcdef]

Six-Coordinate Octahedral
Complexes
ML3L3
Fac isomers have three
identical ligands on the
same face.
Mer isomers have three
identical ligands in a
plane bisecting the
molecule.

Six-Coordinate Octahedral
Complexes
The maximum number of isomers can be
difficult to calculate (repeats).
Placing a pair of ligands in the notation <ab>
indicates that a and b are trans to each other.
[M<ab><cd><ef>], [Pt<pyNH3><NO2Cl><BrI>]

How many diastereoisomers in the above

platinum compound (not mirror images)?
Identify all isomers belonging to Ma 3bcd.

Determining the Number of

Isomers

Determining the Number of

Isotopes
Bailar method
With restrictions (such as chelating agents)
some isomers may be eliminated.
Determine and identify the number if
isomers.
[Ma2b2cd] and [M(AA)bcde]

Combinations of Chelate Rings

Propellers and helices
Left- and right-handed propellers

Examine the movement of a propeller required to

move it in a certain direction.
For a left-handed propeller, rotating it ccw would cause
it to move away ().
For a right-handed propeller, rotating it cw would cause
it to move away ().
This is called handedness. Many molecules possess it.

Tris(ethylenediamine)cobalt(III)
This molecule can be treated like a threebladed propeller.
Look down a three fold axis to determine
the handedness of this complex ion.
The direction of rotation required to pull the
molecule away from you determines the
handedness ( or ).

Do this with you molecule set and rubber

bands.

Determining Handedness for

Chiral Molecules
Complexes with two or more nonadjacent chelate
rings may have chiral character.
Any two noncoplanar and nonadjacent chelate rings can
be used.
Look at Figure 9-14 (Miessler and Tarr).

Molecules with more than one pair of rings may

require more than one label.
Ca(EDTA)2+
Three labels would be required.
Remember that the chelate rings must be noncoplanar,
nonadjacent, and not connected at the same atom.

Linkage (ambidentate) Isomerism

A few ligands may bond to the metal through different
atoms.
SCN- and NO2-

How would you expect hard acids to bond to the

thiocyanate ligand?
Solvents can also influence bonding.
High and low dielectric constants.

Steric effects of linkage isomerism

Intramolecular conversion between linkages.
[Co(NH3)5NO2]+2, Figure 9-19.

Separation and Identification of

Isomers
Geometric isomers can be separated by fractional
crystallization with different counterions.
Due to the slightly different shapes of the isomers.
The fit of the counterion can greatly influence
solubility.
Solubility is the lowest when the positive and negative
charges have the same size and magnitude of charges
(Basolo).

Separation and Identification of

Chiral Isomers
Separations are performed with chiral
counterions. The resulting physical properties
will differ allowing separation.
Rotation of polarized light will be opposite for
two chiral isomers at a specific wavelength.
The direction of optical rotation can change with
wavelength.

Circular Dichroism Meaurement

The difference in the absorption of right and
left circularly polarized light is measured.
Circular dichroism l r

Where l and r are the molar absorption

coefficients for left and right circularly polarized
light.

The light received by the detector is presented

as the difference between the absorbances.
Figure 9-20.

Plane-Polarized Light Measurement

The plane of polarization is rotated when passing
through a chiral substance.
Caused by a difference in the refractive indices of the
right and left circularly polarized light.
l r

The optical rotation illustrates positive value on one

side of the adsorption maximum and negative side on
the other. This is termed as the Cotton effect.

Coordination Numbers and

Structures
Factors considered when determining structures.
The number of bonds. Bond formation is
exothermic; the more the better.
VSEPR arguments
Occupancy of d orbitals.
Steric interference by large ligands.
Crystal packing effect.
It may be difficult to predict shapes.

Low Coordination Numbers (C.N.)

C.N. 1 is rare except in ion pairs in the gas phase.
C.N. 2 is also rare.
[Ag(NH3)2]+, Ag is d10 (how?)
VSEPR predicts a linear structure.
Large ligands help force a linear or near-linear arrangment.
[Mn(N[SiMePh2]2)2] in Figure 9-22.

C.N. 3 is more likely with d10 ions.

Trigonal-planar structure is the most common.
[Cu(SPPh3)3]+, adopts a low C.N. due to ligand crowding.

Coordination Number 4
Tetrahedral and square planar complexes are the
most common.
Small ions and/or large ligands prevent high
coordination numbers (Mn(VII) or Cr(VI)).

Many d0 or d10 complexes have tetrahedral

structures (only consider bonds).
MnO4- and [Ni(CO)4]
Jahn-Teller distortion (Chapter 10)

Coordination Number 4
Square-planar geometry
d8 ions (Ni(II), Pd(II), and Pt(III))
[Pt(NH3)2Cl2]

The energy difference between square-planar

and tetrahedral structures can be quite small.
Can depend on both the ligand and counterion.
More in chapter 10.

Coordination Number 5
Common structures are trigonal bipyramid and
square pyramid.
The energy difference between the two is small. In
many measurements, the five ligands appear identical
due to fluxional behavior.
How would you modify the experiment to differentiate
between the two structures?

Five-coordinate compounds are known for the full

range of transition metals.
Figure 9-27.

Coordination Number 6
This is the most common C.N. with the
most common structure being octahedral.
If the d electrons are ignored, this is the
predicted shape.
[Co(en)3]3+

This C.N. exists for all transition metals (d 0

to d10).

Distortions of Complexes
Containing C.N. 6
Elongation and compression (Fig. 9-29).
Produces a trigonal antiprism structure when the angle
between the top and bottom triangular faces is 60.
Trigonal prism structures are produced when the faces
are eclipsed.
Most trigonal prismatic complexes have three bidentate
ligands (Figure 9-30).
interactions may stabilize some of these structures.

The Jahn-Teller effect (Ch. 10) is useful in predicting

observed distortions.

Higher Coordination Numbers

C.N. 7 is not common
C.N. 8
There are many 8-coordinate complexes for
large transition elements.
Square antiprism and dodecahedron

C.N.s up to 16 have been observed.