Coordination complex: A structure containing a metal

(usually a metal ion) bonded (coordinated) to a group of

surrounding molecules or ions.

Ligand (ligare is Latin, to bind): A ligand is a molecule or

ion that is directly bonded to a metal ion in a
coordination complex

A ligand uses a lone pair of electrons (Lewis base)

to bond to the metal ion (Lewis acid)

Coordination sphere: A metal and its surrounding ligands

Note: religare is Latin, to bind tightly

1
 Complex ions:
Three common structural types

Octahedral:
Tetrahedral Square planar
Most important

2
 The formation of a coordinate complex is a Lewis acid-
base reaction

Lewis base: NH3 Coordination complex:

Lewis base coordinated
to a Lewis acid

Coordination complex:
Ligand (electron donor)
coordinated to a metal
Lewis acid: Co3+ (electron acceptor)

The number of ligand bonds to the central metal atom is

termed the coordination number 3
 The basic idea is that the ligand (Lewis base) is
providing electron density to the metal (Lewis acid)

The bond from ligand to metal is covalent (shared pair), but both
electrons come from the ligand (coordinate covanent bond)

In terms of MO theory we visualize the coordination as the

transfer of electrons from the HO of the Lewis base to the LU of
the Lewis acid

Lewis base Lewis acid

HO LU

NH3 Co3+
4
 Types of Ligands:
Monodentate (one tooth) Ligands
Latin: “mono” meaning one and “dens” meaning tooth

5
 Types of Ligands:
Bidentate (two teeth) Ligands

Bidentate (chelates):

6
 Types of Ligands: Ethylenediaminetetraacetate ion
(EDTA): a polydentate chelating ligand

Chelate from
Greek chela, “claw”

EDTA wraps around the metal ion at

all 6 coordination sites producing an
exceedingly tight binding to the
metal

7
 Alfred Werner: the father of
the structure of coordination
complexes

The Nobel Prize in Chemistry 1913

"in recognition of his work on the
linkage of atoms in molecules by which
he has thrown new light on earlier
investigations and opened up new fields
Alfred Werner of research especially in inorganic
Switzerland chemistry"
University of Zurich
Zurich, Switzerland
b. 1866
(in Mulhouse, then Germany)
d. 1919
8
 Lewis acids and bases

A Lewis base is a molecule or ion that donates a lone pair

of electrons to make a bond

Examples: NH3 OH2 Cl

-
F
-

Electrons in the highest occupied orbital (HO) of a

molecule or anion are the best Lewis bases

A Lewis acid is a molecule of ion that accepts a

lone pair of electrons to make a bond
+ 3+ 2+ n+
Examples: H Co Co M

Molecules or ions with a low lying unoccupied orbital (LU)

of a molecule or cation are the best Lewis acids 9
 Conventions in writing the structure of
coordination compounds:
A coordination compounds is a neutral species
consisting of a coordinate complex and uncoordinated
ions required to maintain the charge balance

Brackets [] are used to indicate all of the

composition of the coordinate complex

The symbol for the central atom metal of the

complex is first within the brackets

Species outside of the [] are not coordinated to the

metal but are require to maintain a charge balance
10
 Werner’s explanation of coordination
complexes
Metal ions exhibit two kinds of valence: primary and
secondary valences

The primary valence is the oxidation number (positive

charge) of the metal (usually 2+ or 3+)

The secondary valence is the number of atoms that

are directly bonded (coordinated) to the metal

The secondary valence is also termed the “coordination

number” of the metal in a coordination complex
11
 Example of a coordination complex:
[Co(NH3)6]Cl3
What is the atomic
[Co(NH3)6]
composition of the
complex?

What is the net charge

of the complex? [Co(NH3)6]3+

How do we know the charge 3+ is required to balance

is 3+ on the metal? the three Cl- ions

The primary valence of [Co(NH3)6]Cl3 is 3 (charge on Co)

The secondary valence of [Co(NH3)6]Cl3 is 6 (ligands) 12
 Structures of Coordination Complexes:
The ammonia complexes of Co(III) = Co3+
How did Werner deduce the structure of coordination complexes?

Composition Ions released Color

CoCl3.6NH3 3 “free” Cl- ions Orange-Yellow

CoCl3.5NH3 2 “free” Cl- ions Purple

CoCl3.4NH3 1 “free” Cl- ions Green

CoCl3.3NH3 0 “free” Cl- ions Green

In all of these complexes there is no free NH3

(No reaction with acid) 13
 Logic: Cl- is not in coordination sphere; NH3 is in sphere

Compound 1: CoCl3.6NH3 = [Co(NH3)6]3+(Cl-)3 = [Co(NH3)6](Cl)3

Conclude: 3 free Cl- ions, [Co(NH3)6]3+

Compound 2: CoCl3.5NH3 = [Co(NH3)5Cl]2+(Cl-)2 = [Co(NH3)5Cl](Cl)2

Conclude: 2 free Cl- ions, [Co(NH3)5Cl]2+

Compound 3: CoCl3.4NH3 = [Co(NH3)4Cl2]1+(Cl-) = [Co(NH3)4Cl2](Cl)

Conclude: 1 free Cl- ion, [Co(NH3)4Cl2]1+

Compound 4: CoCl3.3NH3 = [Co(NH3)3Cl3]

No free Cl- ions 14

 Coordination complexes:
Three dimensional structures
NH3 Cl
CoCl3.6NH3 H3N Co NH3 CoCl3.5NH3 H3N Co NH3
H3N NH3 H3N NH3
NH3 NH3
Cl- Cl- Cl- Cl- Cl-

Cl Cl
H3N Co Cl H3N Co NH3
CoCl3.4NH3 H3N NH3 H3N NH3
Isomers!
NH3 Cl
Cl- Cl-

Co Co NH3
H3N

Bond toward you Bond away from you 15

 Isomerism
• Two or more compounds with the same molecular
formula but different arrangements of the atoms
are called isomers.
• Isomers usually have different physical and
chemical properties.
• Coordination compounds exhibit the same types of
isomers as organic compounds, as well as several
kinds that are unique.
• There are 2 main forms of isomerism: structural
isomerism and stereoisomerism.

16
17
Structural/Constitutional
Isomerism

18
19
 Ionization Isomers

Ionization isomers are identical except for a ligand has exchanged place with
an inion or a neutral molecule that was originally outside the coordination
sphere, the central ion and the other ligands are identical. Because the anion
or the molecule outside the coordination sphere is different, the chemical
properties of the isomers are different.

20
 Hydrate (Solvent) Isomers:

Water in outer sphere (water

that is part of solvent)

Water in the inner sphere

water (water is a ligand in
the coordination sphere
of the metal)

A hydrate isomer is a specific kind of ionization

isomer where a water molecule is one of the
molecules that exchange places. 21
Hydrate (Solvent) Isomers:

22
 Linkage (Ambidentate) Isomers

Example: S C N Bonding to metal may occur at

the S or the N atom

Bonding occurs from

N atom to metal

Bonding occurs from

S atom to metal

23
 Linkage (Ambidentate) Isomers

[Co(NH3)5(NO2)]Cl2 [Co(NH3)5(ONO)]Cl2
Pentaamminenitrocobalt(III) Pentaamminenitritocobalt(II
chloride I) chloride
 Coordination Isomerism
The definition of coordination isomerism depends on the
context. Historically, a complete series of coordination
isomers required at least two metals. The ligand:metal ratio
remains the same, but the ligands attached to a specific metal
ion change. E.g. for the empirical formula Pt(NH3)2Cl2, there
are three coordination isomers possible:

Coordination isomers can also be composed of different metal

ions, or the same metal ion in different oxidation states

25
Stereo/Configurational
Isomerism

26
27
• 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 trans-diamminedichloroplatinum(II)
– How about tetrahedral complexes?
– Chelate rings commonly impose a ‘cis’ structure.
Why?
28
 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 Ma3bcd.
Determining the Number of Isomers
 Determining the Number of Isomers

• 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]
 Stereoisomers:
geometric isomers (cis and trans)
Cl Cl
H3N Co NH3 H3N Co Cl
H3N NH3 H3N NH3
Cl NH3

Cl-
Cl-

34
 Cis-trans isomers and beyond

Beyond cis and trans isomers

Cl Cl
CoCl3.3NH3 H3N Co Cl H3N Co Cl
H3N Cl H3 N NH3
NH3 Cl

35
 Optical isomers: enantiomers

Enantiomers are mirror images which are not superimposable

Enantiomers do not have a plane of symmetry

Any molecule which possesses a plane of symmetry is

superimposable on its mirror image

Enantiomers rotate polarized light in different directions;

therefore, enanotiomers are also termed “optical
isomers”
36
 Enantiomers: non superimposable mirror images

A structure is termed chiral if it is not superimposable on

its mirror image

Structure Mirror image

Of structure

Two chiral structures: non superimposable mirror images

37
 Examples of enantiomers

NH3 NH3
H3N Co Cl Cl Co NH3
H2 O Cl Cl H2O 38
H2O H2O
EDTA complexes are optically active

39
 Chirality: the absence of a plane of symmetry
Enantiomers possible

If a molecule possess a plane of symmetry it is achiral

and is superimposible on its mirror image
Enantiomers NOT possible

NH3 NH3 NH3

Cl Co H2O H3N Co Cl Cl Co NH3
Cl H2O H2 O Cl Cl H2O
NH3 H2O H2O

Plane of symmetry No plane of symmetry

Achiral (one structure) Chiral (two enantiomer)
40
Which are enantiomers (non-superimposable mirror images)
and which are identical (superimposable mirror images)?

41
Coordination Complexes in Living Systems

Porphines, hemes, hemoglobin

Photosynthesis: electron transfer

Vitamin B12

42
Porphines and hemes: important molecules in living systems
These planar molecules have a “hole” in the center which to which a
metal can coordinate

Porphine (C20H14N4)) heme (C34H32N4O4Fe))

43
 Why do we need to eat d metals?

Some critical enzymes in our cells are metalloproteins,

giant biolmolecules which contain a metal atom

These metalloproteins control key life processes such

as respiration and protect cells against disease

Hemoglobin is a metalloprotein which contains an iron

atom and transports O2 through out living systems

Vitamin B12, which prevents pernicious anemia, contains

a Co atom which gives the vitamin a red color

44
 Reversible addition of O2 to hemoglobin

The mechanism by which oxygen is carried throughout

the body
45
Involved in many important biological processes,
including the production of red blood cells

Vitamin B12 (Co[C62H88N13O14P])CN 46

A very important porphine that converts solar
photons into food energy: chlorophyll

Chlorophyll (C55H72N4O5Mg) 47