Coordination Chemistry

Department of Chemistry
School of Science
Beijing Institute of Technology

Hui Li
Questions 1: What are the four fundamental branches of
chemistry?

inorganic chemistry
organic chemistry
analytical chemistry
physical chemistry
Active research is performed in border areas towards organic
chemistry, catalysis, materials, biochemistry and physics.
Chapter 1. Introduction
Chapter 2. The Electronic Structure Theory of
Coordination Compound
Chapter 3. Electronic Spectra of Coordination
Compound
Chapter 4. Structure and Properties of Coordination
Compound
Chapter 5. Kinetics and Mechanism of Reactions of
Coordination Compound
Textbook:
《配位化学（双语版） (Bilingual) 》，李晖编著，化学工业出版社（ 2
006 年 2 月版）。

References:
1. “Metals and Ligands Reactivity” - Constable - VCH Publishers.
2. “Advanced Inorganic Chemistry” - Cotton, Wilkinson, Murillo and
Bochmann - Wiley. 
3. “Inorganic Chemistry, Principles of Structure and Reactivity” - Huh
eey, Keiter and Keiter - Harper Collins College Publishers. 

4. “ 配位化合物的结构和性质”，游效曾 编著， 科学出版社

（ 1992 年 2 月）。
Chapter 1
Introduction
The Origin of Coordination Chemistry
1. Early Coordination Compounds
2. Modern Coordination Chemistry
Conductivities of CoCl3·6NH3 were measured when
the compounds were dissolved in water.

AgNO3(aq) + Cl− (aq) −→ AgCl(s) + NO3− (aq)

How might you explain such data?
Isomers are defined here as compounds that have the
same numbers and types of chemical bonds but differ
in the spatial arrangements of those bonds.
The Modern Coordination Chemistry---
Werner Coordination Chemistry
Front cover pages
(merged) from book on
the life of Werner
Alfred Werner (1866-1919) was appointed
at the University of Zurich to teach organic
chemistry.
In fact, he was very interested in inorganic
chemistry and found many problems to
disturb the inorganic chemists.
Two types of valence:
a primary valence or ionizable, valence corresponded
to what we call today the oxidation state; for cobalt, it
is the 3+ state.
a secondary valence is more commonly called the
coordination number (fixed geometric positions in
space).
Some chloride ions must
do double duty and help
satisfy the both of primary
valence and secondary
valence.
Please distinguish the two concepts of “oxidation
number” and “coordination number”.
The geometry of the
secondary valence

The number of actual

versus predicted
isomers for three
different geometries
How many isomers about
CoCl3·4NH3 ?
 Proposed structure of cobalt ammonia complexes from
number of ionized chloride
solid color ionized Cl- complex formula

CoCl36NH3 Yellow [Co(NH3)6]Cl3

CoCl35NH3 Purple [Co(NH3)5Cl]Cl2
CoCl34NH3 Green trans-[Co(NH3)4Cl2]Cl
CoCl34NH3 Violet cis-[Co(NH3)4Cl2]Cl
Again, checking some interesting compounds:
[Co(en)3]2+
[Co(en)2ClNH3]2+
(en = NH2CH2CH2NH2 is ethylenediammine)
They should exist in two forms, which are mirror
images of each other.

The absolute configuration of [Co(en)3]3+   

Chiral; Chirality
It is a concept relating to a molecule that is not su
perimposable on its mirror image. The one looks lik
e an image in the mirror of the another. These two m
olecules are considered as chiral molecules.
The two chiral molecules have the same physical a
nd chemical properties.

Optical Isomer
Optic isomers is also called enantiomers.
Enantiomers are related as non-superimposable
mirror images and differ in the direction with which
they rotate plane-polarized light.
These isomers are refered to as enantiomers or
enantiomorphs of each other and their non-
superimposable structures are described as being
asymmetric.
Because of the prevailing view that
optical activity was related to C atoms,
Werner prepared a completely chiral
inorganic complex (i.e., no C atoms)
successfully, to prove that "carbon free
inorganic compounds can also exist as
mirror-image isomers".
 Alfred Werner received the Nobel
Prize of Chemistry in 1913 for his
coordination theory of transition
metal-amine complexes.
Coordination chemistry is the study of
compounds formed between metal ions and
other neutral or negatively charged
molecules.
A coordination compound is the product
of a Lewis acid-base reaction in which
neutral molecules or anions (called
ligands) bond to a central metal atom (or
ion) by coordinate bonds.
For example:
A complex is Ag(NH3)2+, formed when Ag+ ions
are mixed with neutral ammonia molecules.
Ag+ + 2 NH3 Ag(NH3)2+
A complex Ag(S2O3)23- is formed between silver
ions and negative thiosulfate ions:
Ag+ + 2 S2O32- Ag(S2O3)23-
 Journal of Coordination Che
mistry
Editors: Jim D. Atwood, Depa
rtment of Chemistry, 556 Natur
al Sciences Complex, North Ca
mpus, SUNY University at Buff
alo, NY 14260-3000 USA
Peter Williams, Centre for Indu
strial and Process Mineralogy, S
chool of Science, Food & Horti
culture, University of Western S
ydney, Locked Bag 1797, Penrit
h South DC, NSW 1797, Austra
lia
Something old and something new,
Something borrowed and something blue,
Something lacy and something racy,
It will definitely be new
And it might just be from you.
 Nomenclature of
Coordination Complexes
 Structures of coordination compounds can be very
complicated, and their names long because the ligands may
already have long names.
Knowing the rules of nomenclature not only enable you to
understand what the complex is, but also let you give
appropriate names to them.
The rules are outlined below:
1. In naming the entire complex, the name of the
cation is given first and the anion second (just as for
sodium chloride), no matter whether the cation or the
anion is the complex species.
2. In the complex ion, the name of the ligand or
ligands precedes that of the central metal atom. (This
procedure is reversed for writing formulae.)
3. Ligand names generally end with 'o' if the ligand is ne
gative ('chloro' for Cl-, 'cyano' for CN-, 'hydrido' for H-).
For neutral ligands, their names are not changed ('methy
lamine' for MeNH2).

Special ligand names are as follow:

H2O, aqua
NH3, ammine (not two m's, amine is for organic
compounds)
CO, carbonyl
NO, nitrosyl
The last "e" in names of negative ions are changed
to "o" in names of complexes. Sometimes "ide" is
changed to "o". Note the following:
Cl-, chloride --> chloro
OH-, hydroxide --> hydroxo
O2-, oxide --> oxo
O22- peroxide, --> peroxo
CN-, cyanide --> cyano
bromide (Br-) ----> Bromo
nitrite (NO22-) ----> nitrito (M – O bond)
nitro (M – N bond)
carbonate (CO32-) ----> carbonato
oxalate (C2O42-) ----> oxalato
sulfate (SO42-) ----> sulfato
thioSulfate (S2O32-) ----> thiosulfato
N3-, azide -> axido;
NH2-, amide -> amido
CO32-, carbonate -> carbonato
-ONO2-, nitrate -> nitrato (when bonded through O)
-NO3-, nitrate -> nitro (when bonded through N)
S2-, sulfide -> sulfido
SCN-, thiocyanate -> thiocyanato-S
NCS-, thiocyanate -> thiocyanato-N
-(CH2-N(CH2COO-)2)2, ethylenediaminetetraacetato (EDT
A)
4. A Greek prefix (mono, di, tri, tetra, penta, hexa,
etc.) indicates the number of each ligand (mono i
s usually omitted for a single ligand of a given typ
e). If the name of the ligand itself contains the term
s mono, di, tri, for example, triphenylphosphine, th
en the ligand name is enclosed in parentheses and i
ts number is given with the alternate prefixes bis, tr
is, tetrakis instead.
For example, Ni(PPh3)2Cl2 is named dichloro
bis(triphenylphosphine)nickel(II).
Greek prefix: mono-, di- (or bis), tri-, tetra-,
penta-, hexa, hepta-, octa-, nona-, (ennea-), d
eca- etc for 1, 2, 3, ... 10 etc.
5. A Roman numeral or a zero in parenthese
s is used to indicate the oxidation state of the
central metal atom.
6. If the complex ion is negative, the name of the metal
ends in 'ATE' for example, ferrate, cuprate, nickelate, c
obaltate etc.
7. If more than one ligand is present in the species, the
n the ligands are named in alphabetical order regardless
of the number of each. For example, NH3 (ammine) wo
uld be considered an 'a' ligand and come before Cl- (chl
oro). (This is where the 1971 rules differ from the 1957
rules. Some texts still say that ligands are named in the
order: neutral then anionic).
If complexes is an anion, its name ends with –ate
appended to either the English or Latin name of the
metal. Example:
Scandium, Sc = scandate Trtani
um, Ti = trtanate vanadium, V =
vanadate chromium, Cr = chrom
ate manganese, Mn = manganat
e iron, Fe = ferrate cob
alt, Co = cobaltate nickel, N
i = nickelate copper, Cu =
cuprate zinc, Zn = zincat
e
Some additional notes:
(i) Some metals in anions have special names
B: Borate; Au: Aurate; Ag: Argentate; Fe: Ferrate;
Pb: Plumbate; Sn: Stannate; Cu: Cuprate
(ii) Use of brackets or enclosing marks.
Square brackets are used to enclose a complex ion or
neutral coordination species. Examples:
[Co(en)3]Cl3; [Co(NH3)3(NO2)3]; K2[CoCl4]
Normal names that will not change
C5H5N, pyradine
NH2CH2CH2NH2, ethylenediamine
C5H4N-C5H4N, dipyridyl
P(C6H5)3, triphenylphosphine
NH2CH2CH2NHCH2CH2NH2, diethylenetriamine
Please try to give the name of the following molecules:
[Co(NH3)5Cl]Cl2, Pentaamminechlorocobalt(III) chloride
[Cr(H2O)4Cl2]Cl, Tetraaquodichlorochromium(III) chloride
K[PtCl3NH3], Potassiumamminetrichloroplatinate(II)
PtCl2(NH3)2, Diamminedichloroplatinum
Co(en)3Cl3, Tris(ethylenediamine)cobalt(III)chloride
Ni(PF3)4, Tetrakis(phosphorus(III)fluoride)nickel
(0)
(iii) A bridging ligand is indicated by placing a m- befo
re its name. The m- should be repeated for every bridgi
ng ligand.
For example: 
(H3N)3Co(OH)3Co(NH3)3,
Triamminecobalt(III)-m-trihydroxotriamminecobalt(III)
Please try to give the structural formula for chlor
otriphenylphosphinepalladium(II)-m-dichlorochl
orotriphenylphosphinepalladium(II).

The structure is

Cl
(C 6 H5 )3 P Cl
Pd Pd
Cl P(C 6H 5 )3
Cl
Questions for the above structure:
1.How many ionized chloride ions are there per
formula?
2. How many chloride ions act as bridges per formula
in this complex?
3. How many types of chloride ligands are there in
this complex?
 Name the complex:
H
N
(en)2 Co Co(en)2 Cl3
O
H

The name is Bis(ethylenediamine)cobalt(III)-m- imi

do-m-hydroxobis(ethylenediamine)cobalt(III) ion.
Questions:
1. When this compound dissolves in water, is the
solution a conductor? What are the ions present in
the solution of this compound? How many moles
of chloride ions are present per mole of the comp
ound?
2. When potassiumtrichloroammineplatinate(II) d
issolves in water, what ions are produced? What a
bout chloropentaamminecobalt(III) chloride?
For the complex K3[Cr(C2O4)3]·3H2O
1) What is the central metal ion?
2) What is its oxidation state?
3) What is its electronic configuration?
4) What is its coordination number?
5) What is the shape of the ion?
6) Can the structure have isomers?
7) Draw one isomer.
8) What is the IUPAC name of the complex?
 For the complex K3[Cr(C2O4)3].3H2O

1) Central metal is Chromium

2) O.S. is III
3) electronic configuration is d3
4) C.N. is 6 (3 bidentate ligands present)
5) structure is octahedral
6) Yes, optical isomers are possible
7) one isomer is shown
8) Potassium tris(oxalato)chromate(III) trihydrate
Coordination Number
The total number of points of attachment to the central
element is termed the coordination number.
This can vary from 2 to as many as 16, but is usually 6.
 Coordination Number 2
This arrangement is not very common for first row t
ransition metal ion complexes and some of the best
known examples are for Silver(I).

For instance, a method often employed for the detec

tion of chloride ions involves the formation of the li
near diamminesilver(I) complex.
The first step is:
Ag+ + Cl- AgCl (white ppt)
and to ensure that the precipitate is really the chloride sal
t, two further tests must be done:
AgCl + 2NH3 [Ag(NH3)2]+ 

and 

[Ag(NH3)2]+ + HNO3 AgCl (re-ppts)

 Coordination Number 3
Once again, this is not very common for first row transition metal
ions. Examples with three different geometries have been
identified:

Trigonal planar Trigonal pyramid T-shaped

Trigonal planar
Well known for main group species like CO32- etc, this geometry
has the four atoms in a plane with the bond angles between the
ligands at 120 degrees.

Trigonal pyramid
More common with main group ions.

T-shaped
The first example of a T-shaped molecule was found in 1977.
 Coordination Number 4
Two different geometries are possible. The tetrahedron is the
more common while the square planar is found almost exclusively
with metal ions having a d8 electronic configuration.
Tetrahedral
The chemistry of molecules centred around a tetrahedral C
atom is covered in organic courses.
However, there are large numbers of tetrahedral Cobalt(II)
complexes known.

Square Planar
This is fairly rare and is included only because some extre
mely important molecules exist with this shape.
 Coordination Number 5

Square pyramid Trigonal Bipyramid

The structure of [Cr(en)3][Ni(CN)5]·1.5H2O was
reported in 1968 to be a remarkable example of a
complex exhibiting both types of geometry in the
same crystal.

The reaction of cyanide ion with Ni2+ proceeds via

several steps:
Ni2+ + 2CN- Ni(CN)2

Ni(CN)2 + 2CN- [Ni(CN)4]2-

orange-red ( log(β4) = 30.1)

[Ni(CN)4]2- + CN- [Ni(CN)5]3-

deep red
Oxovanadium salts (Vanadyl, VO2+ ) often show
square pyramidal geometry, for example,
VO(acac)2.

Note that the Vanadium(IV) can be considered

coordinatively unsaturated and addition of
pyridine leads to the formation of an octahedral
complex.
 Coordination Number 6

Hexagonal planar, Trigonal prism, Octahedral

Hexagonal planar
Unknown for first row transition metal ions, although th
e arrangement of six groups in a plane is found in some
higher coordination number geometries.

Trigonal prism
Most trigonal prismatic compounds have three bidentat
e ligands such as dithiolates or oxalates and few are kno
wn for first row transition metal ions.
Octahedral
The most common geometry found for first row
transition metal ions, including all aqua ions.
In some cases distortions are observed and these
can sometimes be explained in terms of the
Jahn-Teller Theorem.
 Coordination Number 7

Capped octahedron Capped trigonal prism Pentagonal Bipyrami

d
 Coordination Number 8

Dodecahedron (D2d), Cube (Oh), Square antiprism (D4d)

 Coordination Number 9
Three-face centred trigonal prism (D3h)
Coordination Number 10
Bicapped square antiprism (D4d)
Coordination Number 11
All-faced capped trigonal prism (D3h)
Coordination Number 12
cuboctahedron (Oh)
Fuzzy
 Complex Formation Reactions

Mn+ + pLx- M(L)pn-x (L=anion)

or
Mn+ + pL M(L)pn+ (L=molecule)

where Mn+=Lewis acid= center of coordination

and L and Lx-=Lewis bases=ligand(s)
Isomer in Coordination
Chemistry
 Isomers compounds with the same molecular formula
but different arrangements of atoms in space

Stereoisomers
Constitutional(Structural) isomers have some atoms bonded
differ in how the atoms are joined to each other but different
together (have different bonds) spatial arrangements
 Constitutional(Structural) Isomers
Isomers
compounds with the same molecular formula but different
arrangements of atoms in space

Constitutional(Structural) isomers
differ in how the atoms are joined together
(have different bonds)

Linkage isomers
Ionization Isomers
differ in an atom of a ligand
differ in an anion bonded to the metal
bonded to the metal
 Constitutional (Structural) Isomers

Ionization isomers
[Co(NH3)5Br]Cl vs [Co(NH3)5Cl]Br
Linkage isomers
[Co(NH3)5(SCN)]Cl vs [Co(NH3)5(NCS)]Cl
[Co(NH3)5(ONO)]Cl vs [Co(NH3)5(NO2)]Cl
 Stereoisomers
Isomers
compounds with the same molecular but different
arrangements of atoms in space

Stereoisomers
have same atoms bonded to each other but different
spatial arrangements(have same bonds)

Diastereoisomers(Geometric isomers) Enantiomers(Optical isomers)

have same atoms nonsuperimposable mirror images
 Diastereoisomers

Diastereoisomers have diferent chemical and physi

cal proeprties.
Different colors, melting points, polarities, solubili
ties, chemical reactivities, etc.
 Properties of Enantiomers
Most of the properties of two optical isomers are the sa
me
solubility, melting point, boiling point, color, chem
ical reactivity (with nonchiral reagnets)
Two optical isomers differ in their:
(1) Reactivity with other “chiral” reagents
(2) Interactions with plane polarized light