Chemistry 3820 (Fall 2006)

Historical Evolution of Modern Coordination Chemistry

1798 Tassaert (France) CoCl3 in aqueous ammonia pink salt with
the composition CoN6H18Cl3 = CoCl3(NH3 )6.
Over the next 50 years a series of related cobalt, iridium and platinum
compounds was prepared (see below) the nature of these inorganic species
remained a mystery.

Semi-

Colour

Original name

Equivalents of

Number of ions

empirical

AgCl

(+ve or ve)

formula

precipitated

predicted from

upon Ag+

conductivity

addition

measurements

(Blomstrand)

(Werner)

CoCl3(NH3)6

Yellow

Luteocobaltic

CoCl3(NH3)5

Purple

Purpureocobaltic

CoCl3(NH3)4

Green1

Praseocobaltic

CoCl3(NH3)4

Violet1

Violeocobaltic

CoCl3(NH3)3

Orange

This compound has two isomers. One is green (trans-isomer) and the other
is violet (cis-isomer).

2006 - Dr. Paul G. Hayes University of Lethbridge

Chemistry 3820 (Fall 2006)

Conductivities of selected coordination compounds

Formula

conductivity

electrolytes

Werner formulation

[ -1 cm2 mol-1 ]
PtCl42NH3

[Pt(NH3)2Cl4] (trans)

PtCl42NH3

[Pt(NH3)2Cl4] (cis)

NaCl

124

1:1

PtCl43NH3

97

1:1

[Pt(NH3)3Cl3]Cl

PtCl4NH3KCl

107

1:1

K[Pt(NH3)Cl5]

CaCl2

261

1:2

CoCl35NH3

261

1:2

[Co(NH3)5Cl]Cl2

CoBr35NH3

258

1:2

[Co(NH3)5Br]Br2

CrCl35NH3

260

1:2

[Cr(NH3)5Cl]Cl2

CrBr35NH3

280

1:2

[Cr(NH3)5Br]Br2

PtCl44NH3

229

1:2

[Pt(NH3)4Cl2]Cl2

PtCl42KCl

257

2:1

K2[PtCl6]

LaCl3

394

1:3

CoCl3

408

1:3

CoCl36NH3

432

1 :3

[Co(NH3)6 ]Cl3

CoBr36NH3

427

1:3

[Co(NH3)6 ]Br3

CrCl36NH3

442

1:3

[Cr(NH3)6]Cl3

PtCl45NH3

404

1:3

[Pt(NH3)5Cl]Cl3

PtCl46NH3

523

1:4

[Pt(NH3)6]Cl4

2006 - Dr. Paul G. Hayes University of Lethbridge

Chemistry 3820 (Fall 2006)

1862 Blomstrand (Sweden) suggested the structures below:

NH3
Co

NH3
NH3

Cl

Cl

NH3

NH3

NH3

Cl

Co

Cl

NH3
NH3

NH3

NH3

NH3

Cl

Cl
CoCl 3(NH3)5

CoCl 3(NH3 )6

Cl
Co

NH3

NH3

NH3

NH3

Cl

Cl
CoCl3(NH3) 4

Based on measurements of the amount of AgCl precipitated upon Ag+

addition.
Since CoCl3(NH3)6, CoCl3(NH3)5 and CoCl3(NH3 )4 all contain three chloride
groups, but the number of Cl- groups that can be removed by Ag+ differs,
Blomstrand correctly proposed that there must be two different types of
chloride in these complexes.
However, the incorrect structures that he proposed were clearly influenced by
organic chemistry, where the existence of long carbon chains was well
established!

2006 - Dr. Paul G. Hayes University of Lethbridge

Chemistry 3820 (Fall 2006)

1892 Werner (Germany) proposed a different interpretation based on

careful conductivity measurements:
3+

NH 3
CoCl3(NH 3)6 =
[Co(NH3)6]Cl3 =

H3N
H3N

Co

NH 3
NH 3

NH 3
2+

Cl
CoCl3(NH 3)5 =
[CoCl(NH 3)5]Cl2 =

H3N
H3N

Co

NH 3
NH 3

NH 3
1+

Cl
CoCl3(NH 3)4 =
[CoCl2(NH3)4]Cl =

H3N
H3N

Co

NH 3
NH 3

1+

Cl
or

H3N
H3N

Cl
trans

Co

Cl
NH 3

NH 3
cis

The octahedral coordination complexes that Werner proposed agree with

several pieces of experimental evidence:
(1) Precipitation of the correct amount of AgCl upon addition of Ag+ Blomstrands proposed structures also give the same result.
(2) Conductivity measurements - Blomstrands structures cannot explain.
(3) Number of isomers - for an octahedral arrangement of the ligands in
[CoCl2(NH3)4]Cl two possible isomers (cis and trans). This is what is
experimentally observed. Other arrangements of ligands can be envisioned,
but give rise to more than two isomers of [CoCl2(NH3)4]Cl (see below).
2006 - Dr. Paul G. Hayes University of Lethbridge

Chemistry 3820 (Fall 2006)

Alfred Werner

2006 - Dr. Paul G. Hayes University of Lethbridge

Chemistry 3820 (Fall 2006)

Werners ideas become popular.

Needed more evidence to persuade his toughest critics.

Analogue of [CoCl2(NH3 )4]Cl could be prepared using two equivalents of
H2N-CH2-CH2 -NH2 (ethylenediamine = en) in place of four NH3 ligands
The cis-isomer of this complex should be chiral (no mirror planes or centre of
inversion).

Cl
H2
N
N
H2

Co

H2
N
N
H2

H2
N
N
H2

Cl

Cl
Co

Cl
NH2

Cl
Cl
H 2N

H2N

Co

H2
N
N
H2

NH2
cis
(optical isomers)

trans

(1) Werner prepared cis-[CoCl2(en)2]Cl

(2) He then separated both optical isomers
(3) He measured their specific optical rotation.
Blomstrand insisted that he was correct, and that the optical activity of the
compounds that Werner had prepared was due to the carbon atoms of the
ethylenediamine ligands.

2006 - Dr. Paul G. Hayes University of Lethbridge

Chemistry 3820 (Fall 2006)

To prove Blomstrand wrong once and for all, Werner set out to prepare the
first optically active octahedral complex that does not contain carbon.

1913 Werner was awarded the Nobel Prize for his work.
1914 Werner resolved the optical isomers of the complex shown below (the
first optically active complex that does not contain carbon).

Werner had solved the mystery of complex compounds of the transition

metals and brought in the era of modern inorganic chemistry.

6+

NH 3
H 3N
NH 3
H 3N
H 3N

Co
NH 3

HO
H
O
O
H

Co
HO
H 3N

Co

NH3
NH3

OH
OH
Co

NH3
NH3

NH 3

2006 - Dr. Paul G. Hayes University of Lethbridge