Coordination compound

Coordination compound, any of a class of substances with

chemical structures in which a central metal atom is surrounded
by nonmetal atoms or groups of atoms, called ligands, joined to it by
chemical bonds. Coordination compounds include such substances
as vitamin B12, hemoglobin, and chlorophyll, dyes and pigments,
and catalysts used in preparing organic substances.

Coordination compounds contain a central metal atom surrounded by

nonmetal atoms or groups of atoms, called ligands. For example, vitamin
B12 is made up of a central metallic cobalt ion bound to multiple nitrogen-
containing ligands.
A major application of coordination compounds is their use
as catalysts, which serve to alter the rate of chemical reactions.
 Certain complex metal catalysts, for example, play a key role in the
production of polyethylene and polypropylene. In addition, a very
stable class of organometallic coordination compounds has
provided impetus to the development of organometallic chemistry.
Organometallic coordination compounds are sometimes characterized
by “sandwich” structures, in which two molecules of an unsaturated
cyclic hydrocarbon, which lacks one or more hydrogen atoms, bond on
either side of a metal atom. This results in a highly stable aromatic
system.

Key Concepts

 A ligand, or complexing agent, is a polar molecule or an

ion bonded to a central metal ion.
  A complex ion is a polyatomic species consisting of a
central metal ion surrounded by several ligands.
  Naming Complex Ions:

1. Anionic ligands have names ending in 'o'.

'halide' → 'halido', eg, chloride → chlorido

anion ending in 'ate' → 'ato', eg, sulfate → sulfato

anion ending in 'ite' → 'ito', eg, sulfite → sulfito

2. Neutral ligands are named as the molecule without modification, with

these notable exceptions:

H2O → aqua

NH3 → ammine

CO → carbonyl

NO → nitrosyl

3. The numbers of ligands in a complex are specified using the Greek

 prefixes:

di for 2

tri for 3

tetra for 4

penta for 5

hexa for 6

4. The name of a cationic complex ion ends in the name of the central
metal ion with the oxidation state shown as a Roman numeral in
parentheses at the end of the metal's name, eg, iron(III).
5. The name of an anionic complex ion ends in 'ate',
⚛ chromium(II) → chromate(II)
⚛ nickel(II) → nickelate(II)
⚛ platinum(II) → platinate(II)

sometimes the latin name is used, eg,

⚛ silver(I) → argentate(I)
⚛ iron(II) → ferrate(II)
⚛ copper(I) → cuprate(I)
⚛ lead(II) → plumbate(II)
⚛ gold(I) → aurate(I)
⚛ tin(IV) → stannate(IV)

6. Ligands are named before the central metal atom.

  Writing the (Line) Formula of a Complex:

1. Identify the central metal ion

2. Identify the oxidation state on the central metal ion (shown in Roman
numerals parentheses)
3. Identify the ligands
4. Identify the number of ligands
5. Calculate the total charge on the ligands
6. Calculate the charge on the complex ion
    = oxidation state of metal ion + total charge on ligands
7. Write the formula giving the central metal ion first followed by the
ligands, and enclose everything except the charge in square
brackets:

for example, [Mn(H2O)6]2+ and [Fe3(CO)12]

  The coordination number of the complex ion is the

number of bonds formed between the central metal ion and
its ligands.
  The shape (geometry) of a complex ion is related to its
coordination number.

Coordination Possible Shape

Number (Geometry)
2 linear
tetrahedral
4
or square-planar
6 octahedral

Common Ligands

Ligands can be:

  polar molecules (neutral species)

  anions (negatively charged species)

The table below lists some common polar molecules which can be
present as ligands:

Polar Compound Ligand Bonding

Formula
Name Name Atom
Water H2O aqua O
carbon monoxide CO carbonyl C
Ammonia NH3 ammine N
 nitrogen monoxide NO nitrosyl N

The table below lists some anions which can be present as

ligands:

Ion Name Formula Ligand Name Bonding Atom

chloride Cl- chlorido Cl
fluoride F- fluorido F
bromide Br- bromido Br
iodide I- iodido I
hydride H- hydrido H
cyanide CN- cyanido C
hydroxide OH- hydroxido O
thiosulfate S2O32- thiosulfato O
carbonate CO32- carbonato O and O
oxalate C2O42- oxalato O and O

Naming Complex Ions

Example: Name the complex ion with the forumla [Fe(CN)6]3-

1. Anionic ligands have names ending in 'o'.

CN- (cyanide ion) named as cyanido
2. The numbers of ligands in a complex are specified using a
Greek prefix:
6 ligands = hexa → hexacyanido
3. Oxidation state of the central metal atom is shown with a
Roman numeral in parantheses at the end of the metal's
name:
Central metal ion is iron
    oxidation state of iron: 3- = x + (6 × 1-)
    3- = x -6
    x = 3+
Central metal ion: iron(III)
4. The complex ion is an anion, therefore the name will end in
ferrate(III)
 5. Ligands are named before central metal ion:
hexacyanidoferrate(III)

Examples of Names of Complex Ions

No. of
Liga
Ligand Central
nd
Formula s Ion Complex Ion Name
Na
and Name
me
prefix
[Ag(NH3)]2+ ammi 2 → di silver(I) diamminesilver(I) ion
ne +1= x + (complex is a cation)
2(0)
x = +1

[Ag(CN)2]- cyani 2 → di silver(I) → dicyanidoargentate(I)

do argentate(I ion
) (complex is an anion)
-1 = × +
2(-1)
x = +1

[Cu(H2O)62+ aqua 6 → hex copper(II) hexaaquacopper(II)

a +2 = x + ion
6(0) (complex is a cation)
x = +2

[CuCl4]2- chlori 4 → tetr copper(II) tetrachloridocuprate(II

do a → ) ion
cuprate(II) (complex is an anion)
-2 = x +
4(-1)
x = +2

Writing the Formula of Complex Ions

Example: write the formula for the complex ion
tetraamminecopper(II)

1. Identify the central metal ion : copper, Cu

2. Identify the oxidation state of the central metal ion (shown
in parentheses):2+
3. Identify the ligands: ammine = NH3 (neutral species, charge
on ligand = 0)
4. Identify the number of ligands: tetra = 4
5. Calculate the total charge on the ligands:= 4 × 0 = 0
6. Calculate the charge on the complex ion
= oxidation state of metal ion + total charge on ligands =
2+ + 0 = 2+
7. Write the formula giving the central metal ion first followed
by the ligands, everything enclosed in square brackets
followed by the charge on the ion as a superscript:
[Cu(NH3)4]2+

Examples of Formulae of Complex Ions

Central Ligand No. of Complex

Name Ion Formul Ligand Ion
Formula a s Formula
Co2+
(interpretin [Co(H2O)6]2
g oxidation H2O +
hexa =
hexaaquacobalt(II) ion state as a (aqua = (6 × 0) +2
H2O) 6
charge in = 2+)
parenthese
s)

Co2+
(interpretin
tetrachloridocobaltate( g oxidation Cl- [CoCl4]2-
tetra = (4 × -1) +
II) ion state as a (chlorido
= Cl-) 4 2 = 2-
(ate = anion) charge in
parenthese
s)
 Ni2+
(interpretin
g oxidation CO [Ni(CO)4]2+
tetracarbonylnickel(II) tetra = (4 × 0) + 2
state as a (carbony
ion 4
charge in l = CO) = 2+
parenthese
s)

Ni2+
(interpretin
tetracyanidonickelate(I g oxidation CN- [Ni(CN)4]2-
tetra = (4 × -1) +2
I) ion state as a (cyanido
- 4
(ate = anion) charge in = CN ) = 2-)
parenthese
s)

Shapes (Geometry) of Some Complex Ions

  If coordination number (= number of ligands) = 2 then

the shape of the complex ion is linear
  If coordination number (= number of ligands) = 4 then
the shape of the complex ion is tetrahedral or square-planar
  If coordination number (= number of ligands) = 6 then
the shape of the complex ion is octahedral
(octahedral geometry is most common for transition
metal complexes)

Examples of the Shapes of Some Complex Ions

The shape, or geometry, of a number of complex ions is given in

the table below:

Complex Ion No. of Coordination Shape

Formula Ligands Number (Geometry)
[Ag(NH3)2]+ 2 2 Linear
[CuCl2]- 2 2 Linear
[Cr(NH3)6]3+ 6 6 octahedral
 [Fe(CN)6]3- 6 6 octahedral

Coordination Compounds in
Biological System
Naturally occurring coordination compounds are vital to living
organisms. Metal complexes play a variety of important roles in
biological systems. Many enzymes, the naturally occurring catalysts
that regulate biological processes, are metal complexes
(metalloenzymes); for example, carboxypeptidase, a hydrolytic
enzyme important in digestion, contains a zinc ion coordinated to
several amino acid residues of the protein. Another enzyme, catalase,
which is an efficient catalyst for the decomposition of hydrogen
peroxide, contains iron-porphyrin complexes. In both cases, the
coordinated metal ions are probably the sites of catalytic
activity. Hemoglobin also contains iron-porphyrin complexes, its role
as an oxygen carrier being related to the ability of the iron atoms to
coordinate oxygen molecules reversibly. Other biologically important
coordination compounds include chlorophyll (a magnesium-porphyrin
complex) and vitamin B12, a complex of cobalt with a
macrocyclic ligand known as corrin.
 hemoglobin
Hemoglobin is a protein made up of four polypeptide chains (α1, α2, β1, and
β2). Each chain is attached to a heme group composed of porphyrin (an
organic ringlike compound) attached to an iron atom. These iron-porphyrin
complexes coordinate oxygen molecules reversibly, an ability directly related
to the role of hemoglobin in oxygen transport in the blood.
Coordination number
Coordination number is the term proposed by Werner to denote the
total number of bonds from the ligands to the metal atom.
Coordination numbers generally range between 2 and 12, with 4
(tetracoordinate) and 6 (hexacoordinate) being the most common.
Werner referred to the central atom and the ligands surrounding it as
the coordination sphere. Coordination number should be
distinguished from oxidation number (defined in the previous
paragraph). The oxidation number, designated by an Arabic number
with an appropriate sign (or, sometimes, by a Roman numeral in
parentheses), is an index derived from a simple and formal set of rules
and is not a direct indicator of electron distribution or of the charge on
the central metal ion or compound as a whole. For the
hexaamminecobalt(3+) ion, [Co(NH3)6]3+, and the
neutral molecule triamminetrinitrocobalt(3+), [Co(NO2)3(NH3)3], the
coordination number of cobalt is 6 while its oxidation number is +3.
Ligands and chelates
Each molecule or ion of a coordination compound includes a number
of ligands, and, in any given substance, the ligands may be all alike, or
they may be different. The term ligand was proposed by the German
chemist Alfred Stock in 1916. Attachment of the ligands to
the metal atom may be through only one atom, or it may be through
several atoms. When only one atom is involved, the ligand is said to be
monodentate; when two are involved, it is didentate, and so on. In
general, ligands utilizing more than one bond are said to be
polydentate. Because a polydentate ligand is joined to the metal atom
in more than one place, the resulting complex is said to be cyclic—i.e.,
to contain a ring of atoms. Coordination compounds containing
polydentate ligands are called chelates (from Greek chele, “claw”), and
their formation is termed chelation. Chelates are particularly stable
and useful. An example of a typical chelate is bis(1,2-
ethanediamine)copper(2+), the complex formed between the cupric
ion (Cu2+) and the organic
compound ethylenediamine (NH2CH2CH2NH2, often abbreviated as en
in formulas). The formula of the complex is

[Cu(NH2CH2CH2NH2)2]2+

and the structural formula is

Mononuclear, monodentate

The simplest types of coordination compounds are those containing a

single metal atom or ion (mononuclear compounds) surrounded by
monodentate ligands. Most of the coordination compounds already
cited belong to this class. Among the ligands forming such complexes
are a wide variety of neutral molecules (such
as ammonia, water, carbon monoxide, and nitrogen), as well as
monoatomic and polyatomic anions (such as the hydride, fluoride,
chloride, oxide, hydroxide, nitrite, thiocyanate, carbonate, sulfate,
and phosphate ions). Coordination of such ligands to the metal
virtually always occurs through an atom possessing an unshared pair
of electrons, which it donates to the metal to form a coordinate bond
with the latter. Among the atoms that are known to coordinate to
metals are those of virtually all the nonmetallic elements (such as
hydrogen, carbon, oxygen, nitrogen, and sulfur), with the exception of
the noble gases (helium [He], neon [Ne], argon [Ar], krypton [Kr], and
xenon [Xe]).

Polydentate

The chelate complex of a copper ion and ethylenediamine mentioned

above is an example of a compound formed between a metal ion and a
didentate ligand. Two further examples of chelate complexes are
shown below.

These are a nickel complex with a tetradentate large-ring ligand,

known as a porphyrin, and a calcium complex with a hexadentate
ligand, ethylenediaminetetraacetate (EDTA). Because metal-ligand
attachment in such chelate complexes is through several bonds, such
complexes tend to be very stable.
Certain ligands may be either monodentate or polydentate, depending
on the particular compound in which they occur. The carbonate ion,
(CO3)2−, for example, is coordinated to the cobalt (Co3+) ions in two
cobalt complexes, pentaamminecarbonatocobalt(+), [Co(CO3)(NH3)5]+,
and tetraamminecarbonatocobalt(+), [Co(CO3)(NH3)4]+, through one
and two oxygen atoms, respectively.

Polynuclear

Polynuclear complexes are coordination compounds containing two or

more metal atoms, or ions, in a single coordination sphere. The two
atoms may be held together through direct metal-metal bonds,
through bridging ligands, or both. Examples of each are shown above
(see above Polydentate), along with a unique metal-cluster complex
having six metal atoms in its nucleus (see organometallic compound).
Isomerism
Coordination compounds often exist as isomers—i.e., as compounds
with the same chemical composition but different structural formulas.
Many different kinds of isomerism occur among coordination
compounds. The following are some of the more common types.

Cis-trans isomerism

Cis-trans (geometric) isomers of coordination compounds differ from

one another only in the manner in which the ligands are distributed
spatially; for example, in the isomeric pair of
diamminedichloroplatinum compounds

the two ammonia molecules and the two chlorine atoms are situated

next to one another in one isomer, called the cis (Latin for “on this
side”) isomer, and across from one another in the other,
the trans (Latin for “on the other side”) isomer. A similar relationship
exists between the cis and trans forms of the
tetraamminedichlorocobalt(1+) ion:

Enantiomers and diastereomers
So-called optical isomers (or enantiomers) have the ability to rotate
plane-polarized light in opposite directions. Enantiomers exist when
the molecules of the substances are mirror images but are not
superimposable upon one another. In coordination compounds,
enantiomers can arise either from the presence of an
asymmetric ligand, such as one isomer of the amino
acid, alanine (aminopropionic acid),

or from an asymmetric arrangement of the ligands. Familiar examples

of the latter variety are octahedral complexes carrying three didentate
ligands, such as ethylenediamine, NH2CH2CH2NH2. The two
enantiomers corresponding to such a complex are depicted by the
structures below.

The ethylenediamine ligands above are indicated by a curved line

between the symbols for the nitrogen atoms.

Diastereomers, on the other hand, are not superimposable and also

are not mirror images. Using AB as an example of a chelating ligand,
in which the symbol AB implies that the two ends of the chelate are
different, there are six possible isomers of a complex cis-[M(AB)2X2].
For example, AB might correspond to alanine [CH3CH(NH2)C(O)O]−,
where both N and O are attached to the metal. Alternatively, AB could
represent a ligand such as propylenenediamine,
[NH2CH2C(CH3)HNH2], where the two ends of the molecule are
distinguished by the fact that one of the Hs on a C is substituted with
a methyl (CH3) group.
Ionization isomerism

Certain isomeric pairs occur that differ only in that two ionic groups
exchange positions within (and without) the primary coordination
sphere. These are called ionization isomers and are exemplified by the
two compounds, pentaamminebromocobalt sulfate, [CoBr(NH 3)5]SO4,
and pentaamminesulfatocobalt bromide, [Co(SO4)(NH3)5]Br. In the
former the bromide ion is coordinated to the cobalt(3+) ion, and the
sulfate ion is outside the coordination sphere; in the latter the sulfate
ion occurs within the coordination sphere, and the bromide ion is
outside it.

Linkage isomerism

Isomerism also results when a given ligand is joined to the

central atom through different atoms of the ligand. Such isomerism is
called linkage isomerism. A pair of linkage isomers are the ions
[Co(NO2)(NH3)5]2+and [Co(ONO)(NH3)5]2+, in which the anionic ligand
is joined to the cobalt atom through nitrogen or oxygen, as shown by
designating it with the formulas NO2−(nitro) and ONO−(nitrito),
respectively. Another example of this variety of isomerism is given by
the pair of ions [Co(CN)5(NCS)]3− and [Co(CN)5(SCN)]3−, in which an
isothiocyanate (NCS)− and a thiocyanate group (SCN)− are bonded to
the cobalt(3+) ion through a nitrogen or sulfur atom, respectively.

Coordination isomerism

Ionic coordination compounds that contain

complex cations and anions can exist as isomers if the ligands
associated with the two metal atoms are exchanged, as in the pair of
compounds, hexaamminecobalt(3+) hexacyanochromate(3–),
[Co(NH3)6][Cr(CN)6], and hexaamminechromium(3+)
hexacyanocobaltate(3–), [Cr(NH3)6][Co(CN)6]. Such compounds are
called coordination isomers, as are the isomeric pairs obtained by
redistributing the ligands between the two metal atoms, as in the
doubly coordinated pair, tetraammineplatinum(2+)
hexachloroplatinate(2–), [Pt(NH3)4][PtCl6], and
tetraamminedichloroplatinum(2+) tetrachloroplatinate(2–),
[PtCl2(NH3)4][PtCl4].

Ligand isomerism

Isomeric coordination compounds are known in which the overall

isomerism results from isomerism solely within the ligand groups. An
example of such isomerism is shown by the ions, bis(1,3-
diaminopropane)platinum(2+) and bis(1,2-
diaminopropane)platinum(2+),

Bonding theories

Valence bond theory

Several theories currently are used to interpret bonding in

coordination compounds. In the valence bond (VB) theory, proposed
in large part by the American scientists Linus Pauling and John C.
Slater, bonding is accounted for in terms of hybridized orbitals of
the metal ion, which is assumed to possess a particular number of
vacant orbitals available for coordinate bonding that equals
its coordination number. Each ligand donates an electron pair to form
a coordinate-covalent bond, which is formed by the overlap of an
unoccupied orbital of the metal ion and a filled orbital of a ligand. The
configuration of the complex depends on the type and number of
orbitals involved in the hybridization—
e.g., sp (linear), sp3 (tetrahedral), dsp2 (square planar),
and d2sp3 (octahedral), in which the superscripts denote the number of
orbitals of a particular type. In many cases, the number of unpaired
electrons, as determined by magnetic susceptibility measurements,
agrees with the theoretical prediction. The theory was modified in
1952 by the Canadian-born American Nobel chemistry laureate Henry
Taube, who distinguished between inner orbital complexes (d2sp3) and
outer orbital complexes (sp3d2) to account for discrepancies between
octahedral complexes. The main defect of the simple VB theory lies in
its failure to include the antibonding molecular orbitals produced
during complex formation. Thus, it fails to offer an explanation for the
striking colors of many complexes, which arise from their selective
absorption of light of only certain wavelengths. From the early 1930s
through the early 1950s, VB theory was used to interpret almost all
coordination phenomena, for it gave simple answers to the questions
of geometry and magnetic susceptibility with which chemists of that
time were concerned.