Chapter 9

Chemistry of Coordination Compounds

Coordination Chemistry

Alfred Werner (1866-1919)

 1893, age 26: coordination theory
 Nobel prize for Chemistry, 1913
 Addition of 6 mol NH3 to CoCl3(aq)
Conductivity studies
Precipitation with AgNO3

Mie ssle r, Tarr, p. 299

Alfred Werner, 1913 Nobel Prize

Complexes Color
CoCl3•6NH3 Yellow
CoCl3•5NH3 Purple
CoCl3•4NH3 Green
CoCl3•4NH3 Violet

CoCl3•6NH3 + excess Ag+ 3AgCl(s)

CoCl3•5NH3 + excess Ag+ 2AgCl(s)
CoCl3•4NH3 + excess Ag+ 1AgCl(s)
 Werner Coordination Theory
NH3 Cl Cl– attached to NH3 may be dissociated

Co NH3 NH3 NH3 NH3 Cl

NH3 Cl

Compound Moles of ions Moles of AgCl(s)

“CoCl3.6NH3” 4 3
“CoCl3.5NH3” 3 2
“CoCl3.4NH3” 2 1
“CoCl3.3NH3” 0 0
 Two Coordination Compounds of Co(III)

CoCl3.6NH3 CoCl3.5NH3

3 free Cl- 2 free Cl-

per formula per formula

[Co(NH3)6]Cl3 [CoCl(NH3)5]Cl2
 Werner Coordination Theory

• Proposed six ammonia molecules to covalently

bond to Co3+

Compound Moles of ions Moles of AgCl(s)

[Co(NH3)6]Cl3 4 3
[Co(NH3)5Cl]Cl2 3 2
[Co(NH3)4Cl2]Cl 2 1
[Co(NH3)3Cl3] 0 0
 Important Terms

• A ligand is a Lewis base that coordinates to a central

metal atom or ion.
• A donor atom is the atom in a ligand that donate a
lone pair of electrons to form a coordinate covalent
bond.
• A unidentate ligand is a ligand that can bind through
only one atom.
 Important Terms

Typical Simple Ligands

Ion/Molecule Name Name as a Ligand

NH3 ammonia ammine

CO carbon monoxide carbonyl

Cl- chloride chloro

 Important Terms
Typical Simple Ligands

Ion/Molecule Name Name as a Ligand

CN- cyanide cyano

F- fluoride fluoro

OH- hydroxide hydroxo

 Important Terms
Typical Simple Ligands

Ion/Molecule Name Name as a Ligand

nitrogen
NO nitrosyl
monoxide

NO2- nitrite nitro

PH3 phosphine phosphine

 Important Terms
• A polydentate ligand is a ligand that can bind
through more than one donor atom.
• There are known examples of bidentate,
tridentate, quadridentate, quinquedentate,
and sexidentate ligands.

• Chelate complexes are complexes that have a

metal atom or ion and polydentate ligand(s) that
form rings.
 Coordination Chemistry
Definitions
• Coordination compounds
NH3 3+

H3N NH3 3Cl– (counterion)

Co
H3N NH3

NH3

(coordination sphere)
ligand
H

N M
H
H N forms a coordinate covalent bond to the metal
• Example 25-1: For the complex compound
K3[Co(CN)6] the coordination number is
_________, and the coordination sphere is
_______.
You do it!

For the complex compound K3[Co(CN)6] the

coordination number is 6 , and the
coordination sphere is 7 .
Tetrahedral and Square Planar
CN = 4
Octahedral (2 views)

CN = 6
 Chelates

• polydentate ligands are also known as chelating

ligands

• chela = “claw”

• ex: ethylenediamine (en)

H2N-CH2-CH2-NH2
[Co(en)3]
3+
Some Bidentate Ligands
 EDTA4- is a Hexadentate Ligand

O O
- -
O C CH2 H2 C C O

N CH2CH2 N
- O C CH2 H2 C C O
-
O O
[CoEDTA] -
A Porphyrin is a Macrocyclic Ligand

2-

NH N
N N

N HN N N

porphine porphyrin
molecule ligand
Hemoglobin and Myoglobin Contain a Heme
Group
HC CH2 CH3

H 3C CH CH2

N N

Fe
N N

H 3C CH3

HOOC-H2C-H2C CH2-CH2-COOH

Iron Protoporphyrin IX (heme-b)

OxyMb/Hb
 Chelation

The carbonato complex is not stable since a 4-membered

ring is highly strained.
Other examples of chelating agents
Forming 5-membered rings:
5-membered and 6-membered rings are less
strained as illustrated by the example below.
 Forming 6-membered rings:

The above examples are all bidentate ligands. There are

ligands that are capable of attaching to a metal atom via
more than two atoms.
diethylenetriamine is an example of a tridentate ligand

porphyrin (found in heme) is a tetradentate ligand

 Determining Charge on Metal Ion

[Co(NH3)6]Cl3

[Pt(NH3)2Cl2]

K4[FeCl6]

[V(H2O)4(CO3)](ClO4)2
 Nomenclature
Rules for Naming Complex Species
1. Cations (+ ions) are named before anions (- ions).
2. Coordinated ligands are named in alphabetical order.
Prefixes that specify the number of each kind of ligand (di = 2, tri =
3, tetra = 4, penta = 5, hexa = 6, etc.) are not used in
alphabetizing
Prefixes that are part of the name of the ligand, such as in
diethylamine, are used to alphabetize the ligands.
 Nomenclature

3. For complicated ligands, especially those that

have a prefix such as di or tri as part of the
ligand name, these prefixes are used to specify
the number of those ligands that are attached to
the central atom.
bis = 2
tris = 3
tetrakis = 4
pentakis = 5
hexakis = 6
 Nomenclature

4. The names of anion ligands end in the suffix -o.

Examples of ligands ending in –o are:

• Cl- chloro
• S2- sulfido
• O2- oxo
• OH- hydroxo
• CN- cyano
• NO3- nitrato
• SO42- sulfato
 Nomenclature

5. The names of most neutral ligands are

unchanged when used in naming the complex.
There are several important exceptions to this
rule including:
• NH3 ammine
• H2O aqua
• CO carbonyl
• NO nitrosyl
 Nomenclature
6. The oxidation number of a metal that exhibits variable
oxidation states is designated by a Roman numeral in
parentheses following the name of the complex ion or
molecule.
7. If a complex is an anion, the suffix "ate" ends the name.
No suffix is used in the case of a neutral or cationic
complex.
Usually, the English stem is used for a metal, but if this
would make the name awkward, the Latin stem is
substituted.
 ferrate instead of ironate
 plumbate instead of leadate
 Nomenclature

• Name the following compounds:

Na3[Fe(Cl)6]
sodium hexachloroferrate (III)
[Ni(NH3)4(OH2)2](NO3)2
You do it!
tetraamminediaquanickel(II) nitrate
 Nomenclature

• Write formulas for the following compounds:

potassium hexacyanochromate(III)
K3[Cr(CN)6]
tris(ethylenediammine) cobalt(III) nitrate
You do it!
[Co(en)3] (NO3)3
 What’s Wrong?
[Cu(NH3)4]Cl2
tetraamminecopper(II) dichloride
tetramminecopper(II) chloride
[Co(en)2Br2]Cl
dibromodiethylenediaminecobalt(II) chloride

dibromobisethylenediaminecobalt(III) chloride
K[Ag(CN)2]
potassium dicyanidesilver(I)
potassium dicyanoargentate(I)
 Isomerism In Complex Ions
Structural (Constitutional) Isomers
1. Ionization isomers
2. Hydrate isomers
3. Coordination isomers
4. Linkage isomers

Stereoisomers
1. Geometric isomers
2. Optical isomers
 Isomerism in
Coordination Compounds

Structural (Constitutional) Isomers

• Structural isomers involve different atom to ligand
bonding sequences.

• Ionization or Ion-Ion Exchange Isomers

[Pt(NH3)4Cl2]Br2 compared to [Pt(NH3)4Br2]Cl2
Note where the Cl’s and Br’s are in the structures,
that is what makes these two species isomers.
 Ionization Isomers

[Pt(NH3)4Cl2]Br2 [Pt(NH3)4Br2]Cl2

Cl 2- Br 2-
H3 N N H3 H3 N N H3
Pt Pt
H3 N N H3 H3 N N H3
Cl Br
Counter ions Counter ions
are Br-. are Cl-.
 Structural (Constitutional) Isomers
• Hydrate isomers are a special case of ionization
isomers in which water molecules may be changed
from inside to outside the coordination sphere.
• For example:
[Cr(OH2)6]Cl3 vs.
[Cr(OH2)5Cl]Cl2. H2O vs.
[Cr(OH2)4Cl2]Cl2. 2H2O
• Note whether the water molecule(s) are inside or
outside the coordination sphere.
 Hydrate Isomers

[Cr(OH2)6]Cl3 [Cr(OH2)5Cl]Cl2. H2O [Cr(OH2)4Cl2]Cl2. 2H2O

3+ 2+ 1+
OH2 OH2 OH2
OH Cl Cl
H2 O Cr 2 H2 O Cr H2 O Cr
H2 O OH H2 O OH H2 O Cl
OH2 2
OH2 2
OH2

Counter ions Counter ions Counter ions

are 3 Cl-. are 2 Cl- and are 1 Cl- and
1 water. 2 waters.
 Structural (Constitutional) Isomers

• Coordination isomers denote an exchange of

ligands between the coordination spheres of the
cation and anion.
• For example look at these two isomers:
[Pt(NH3)4][PtCl6] vs [Pt(NH3)4Cl2][PtCl4]
• The isomeric distinction is whether the ligands
are on the cation or the anion.
 Coordination Isomers

[Pt(NH3)4][PtCl6] [Pt(NH3)4Cl2][PtCl4]

4 + Cl 4 - Cl 2 + 2 -
H3 N N H3 Cl Cl H3 N N H3 Cl Cl
Pt Pt Pt Pt
H3 N N H3 Cl Cl H3 N N H3 Cl Cl
Cl Cl
 Structural (Constitutional) Isomers

• Linkage isomers have ligands that bind to the

metal in more than one way.
cyano -CN- compared to isocyano -NC-
nitro -NO2- compared to nitrito -ONO-
• For example:
[Co(NH3)5ONO]Cl2 vs. [Co(NH3)5NO2]Cl2
• Note which atom in the ligand is bound to the
central metal atom.
Linkage Isomerism - This happens when a
particular ligand is capable of coordinating to a metal in
two different and distinct ways. Here is an example:
Linkage Isomers
 Stereoisomers

• Stereoisomers are isomers that have different

spatial arrangements of the atoms relative to the
central atom.
• Complexes with only simple ligands can occur as
stereoisomers only if they have coordination
numbers equal to or greater than four.
 Stereoisomers

• Geometrical or positional isomers are

stereoisomers that are not optical isomers.
• Cis-trans isomers have the same kind of ligand
either adjacent to each other (cis) or on the
opposite side of the central metal atom from each
other (trans).
• Note where the ligands are positioned relative to
the central atom.
 Geometric Isomers

cis-[Pt(NH3)2Cl2] trans-[Pt(NH3)2Cl2]
cisplatin
an anticancer drug ~no anticancer effects!
 More Geometric Isomers

cis-[Co(NH3)4Cl2]+ trans-[Co(NH3)4Cl2]+
Geometric Isomerism
In An
Octahedral Complex
 Stereoisomers

• Other types of isomerism can occur in octahedral

complexes.
• Complexes of the type [MA2B2C2] can occur in
several geometric isomeric forms:
trans- trans- trans-
cis- cis- cis-
cis- cis- trans-
 Stereoisomers
trans-diammine-trans-diaqua-trans-dichlorocobalt(III) ion

N H3
H2O Cl
Co
Cl O H2
NH 3
 Stereoisomers
cis-diammine-cis-diaqua-cis-dichlorocobalt(III) ion

N H3
H2O Cl
Co
H3N Cl
O H2
 Stereoisomers
trans-diammine-cis-diaqua-cis-dichlorocobalt(III) ion

N H3
H2O Cl
Co
H2O Cl
NH3
 Stereoisomers

cis-diammine-cis-diaqua-trans-dichlorocobalt(III) ions
You do it!

Cl
H2O NH3
Co
H2O N H3
Cl
 Stereoisomers
cis-diammine-trans-diaqua-cis-dichlorocobalt(III) ions
You do it!

O H2
Cl N H3
Co
Cl N H3
O H2
Geometric Isomers for [CoCl3Br3]3-

fac mer
facial meridional
 Geometric Isomers:
Tetrahedral Complexes

No geometric isomers!
(Each ligand is about the same distance
from the other three.)
In a tetrahedral arrangement, ligands occupy corners of a
tetrahedron. These corners are all adjacent to each other,
therefore, tetrahedral complexes are not capable of
geometric isomerism. Enantiomers, however, are possible,
when all four ligands are different.
 Stereoisomers

• Optical isomers are mirror images of each other that are

not superimposable.
• The cis-diammine-cis-diaqua-cis-dichlorocobalt(III) ion
has two different forms called optical isomers or
enantiomers.
 Optical Isomers
• These are the optical isomers of:
cis-diammine-cis-diaqua-cis-dichlorocobalt(III) ion

N H3 N H3
H2O Cl Cl O H2
Co Co
H3N Cl Cl N H3
O H2 O H2
Optical Isomers
 [M(en)3] is Chiral
n+

N N
N N N N
M M
N N N N
N N
Example 1

mirror plane

cis-[Co(en)2Cl2]+
Example 1
rotate mirror image 180°

180 °
Example 1 nonsuperimposable

cis-[Co(en)2Cl2]+
 Optical Isomers

polarizing filter
plane
polarized optically active sample
light in solution

Dextrorotatory (d) = right

rotation
Levorotatory (l) = left rotation
Racemic mixture = equal
rotated polarized
amounts of two enantiomers; no
light
net rotation