Complexes of metal ions and

nomenclature for inorganic

compounds
Cobalt(III) ion

ammonia ligands

blue = nitrogen
donor atom

[Co(NH3)6]

3+

white =
hydrogen atom

Complexes of metal ions.

Prior to the work of Werner on
coordination complexes,
formulated at the time as
CoCl3.6NH3, for example, there
was no understanding of why
the six ammonia molecules
were so strongly bound in this
compound. Werner showed
that the ammonia molecules
were in fact chemically bound
to the cobalt, and that the three
Cl- ions were present only to
act as counter-ions to the 3+
charge on the [Co(NH3)6]3+
cation.

Alfred Werner (1866-1919)

Nobel prize 1913 for his work
on Coordination compounds

(a)

(b)

[Co(NH3)6]3+

[Co(NH3)5Cl]2+

(c)

[Co(NH3)3Cl3]

Werner proposed that Co(III) (trivalent cobalt) had a coordination

number of six, which could be satisfied by six ammonias in a, five
ammonias and a Cl- in b, and three ammonias and three Cl- in c.
His theory explained why conductivity showed that in solution a
was a 3+ cation, b was a 2+ cation, and c was neutral. The
molecules or ions coordinated to the Co(III) are called ligands, from
the Latin ligare meaning to join. The coordination geometry of the
Co(III) is octahedral, which means that the six ligands are placed
around the Co(III) at the corners of an octahedron.

Some complexes of metal ions:

nickel
Cobalt

water molecule

cyanide
ion

ammonia

2+

nickel

2+

2C

[Co(H2O)6]2+

N
[Ni(NH3)6]2+

[Ni(CN)4]2-

Hexaaquacobalt(II)
hexamminenickel(II)
tetracyanonickelate(II)
A complex is written such that everything inside the square brackets is
a ligand chemically bonded to the metal ion. Everything outside the brackets
is a counter-ion or something simply present in the crystal lattice. Thus, we
might have [Co(H2O)6](NO3)2 where the NO3- ions are counter-ions.

Formal Oxidation State:

The formal oxidation state of metal ions
in their complexes is determined by
ascribing formal charges to all ligands
which correspond to those they
possess as the free molecules or ions:
Neutral: NH3, H2O, CO, PH3, (CH3)2S
Anionic: OH-, F-, Cl-, Br-, I-, CN-, SCNCationic: NO+

Examples of oxidation states:

[Co(NH3)6]3+
=
Co(III)
hexamminecobalt(III)

K3[Fe(CN)6]

Fe(III)

potassium hexacyanoferrate(III)

[Co(NH3)4Cl2]Cl

Co(III)

tetrammiinedichlorocobalt(III) chloride

[FeNO(NH3)5]Cl3 =

Fe(II)

pentamminenitrosyliron(II) chloride

[Cr(CO)6]

Cr(0)

V(-I)

hexacarbonylchromium(O)

K[V(CO)6]

potassium hexacarbonylvanadate(-I)

[Mn(NO)3CO]

trinitrosylcarbonylmanganese(-III)

Mn(-III)

Identifying which are ligands:

In the formula for a complex, everything inside the
square brackets (blue in formula below) is
coordinated to the metal ion, everything outside
(red) is a counterion or a lattice molecule.
When the name of a complex is written, all the
ligands that are coordinated to the metal ion come
before it, while counter-ions come after the name of
the metal:
[Co(NH3)4Cl2]Cl is:
ligands bonded to metal ion

counterion

tetramminedichlorocobalt(III)chloride

Naming of ligands in complexes:

Neutral ligands:
When naming a complex, the ligands are indicated by
names as follows:
Neutral ligands:
NH3
H2O
=
aqua
CO =
carbonyl

ammine

The number of each type of ligand present is indicated by

the Latin prefixes di-, tri-, tetra-, penta-, hexa-, hepta-,
octa-, nona-, and deca-:
[Co(NH3)6]Cl3
[La(H2O)9](NO3)3
nitrate
K2[Ti(CO)6]
titanate(-II)

=
=

hexamminecobalt(III) chloride
nona-aqua lanthanum(III)

potassium hexacarbonyl

Naming of ligands in complexes: anionic

ligands:
Anionic ligands: To indicate that they are anions, ligands
in complexes are given an o ending: fluoro, chloro, bromo,
iodo, hydroxo, cyano, sulfato, nitro, etc. If the overall
charge on the complex is negative, the metal ion is given
an ate ending to indicate this:
K3[Fe(CN)6]

K4[Fe(CN)6]
Na3[AlF6]
[Co(NH3)3F3]

=
=
=

potassium hexacyanoferrate(III)
or potassium hexacyanoiron(III)
potassium hexacyanoferrate(II)
sodium hexafluoroaluminate(III)
triamminetrifluorocobalt(III)

Nomenclature of complexes:
Cations, including complex cations, come first, anions,
including complex anions come second:

[Co(NH3)6]Cl3
Na3[CrCl6]
[Ni(H2O)6]Cl2
K3[Rh(CN)6]

= hexammine cobalt(III) chloride,

= sodium hexachlorochromate(III),
= hexaaquanickel(II) chloride
= potassium hexacyanorhodate(III)

[Co(NH3)6][Co(CN)6] = hexamminecobalt(III)
hexacyanocobaltate(III)

Naming more complex ligands:

Many ligands are more complex and have more than one donor
atom, such as en (ethylenediamine), bipy (2,2-bipyridyl) and acac
(acetyacetonate) below:

H3C
H2N

NH2
N
en

bipy

CH3
O

O-

acac

Where more complex ligands are present, one indicates the

number of these present with prefixes bis-, tris-, tetrakis, pentakis,
or hexakis, followed by the name of the ligand in parentheses.
Thus, [Co(en)3]Cl3 is tris(ethylenediamine)cobalt(III) chloride.

Some cobalt(III) complexes of more

complex ligands:
CH3

H2N

NH2 H
2
N

Co
H2N
NH2

N
H2

.Cl3

tris(ethylenediamine)
cobalt(III)chloride

CH3

Co

Co

H3C

H3C

.(NO3)3

tris(2,2-bipyridyl)
cobalt(III) nitrate

O
O

CH3

CH3

tris(acetylacetonato)
cobalt(III)

NOMENCLATURE
1.1 Formulas of Simple Ionic substances.
For ionic compounds, the cation (more
electropositive element) should always
be first. (KCl, Na2S). If several cations
are present, they should be listed in
alphabetical order, followed by anions
in alphabetical order (LiMgClF2). An
exception is the proton, which is always
listed last in the sequence of cations,
(RbHF2).

Nomenclature (contd.)
1.2. Sequence of atoms in formulas of
polyatomic ions and molecules:
For polyatomic species with a central atom,
these are generally listed first followed by the
attached atoms in alphabetical order (SO42-,
CCl2H2, PCl3O, SO3, -CF3, -SCN). An exception
is the linear thiocyanate group
(-SCN),
where the atoms are placed in the order in
which they occur in the thiocyanate ion:
-S=C=N

Formulas and Names of Common substances.

Acid

Name

Name of anion

HNO3

Nitric acid

nitrate

H3PO4

Phosphoric acid

phosphate

H2SO4

Sulfuric acid

sulfate

HClO4

Perchloric acid

perchlorate

HClO3

Chloric acid

chlorate

HClO2

Chlorous acid

chlorite

HClO
HCl

Hypochlorous acid
Hydrochloric acid

hypochlorite
chloride

Chemical Names
Names of the Elements: These originated
with Berzelius (1813) who developed the
system that the symbol for an element was
the first letter of its name, e.g., F, O, N, C, B. If
there was more than one element whose
name started with the same letter, then a
second, lower-case letter, was added, which
was usually the second letter of the name of
the element. e.g. C for carbon, but Ca, Cd,
Ce, Cf, Cl, Cm, Co, Cr, Cs, Cu. B for Boron,
but Ba, Be, Bi, Bk, Br, and so on.

Names of metallic elements you should

know (pretty much all of them):
H
hydrogen

Li

Be

lithium

beryllium

Na

Mg

sodium

magnesium

Ca

Sc

Ti

potassium

calcium

scandium

titanium

vanadium

Rb

Sr

Zr

Nb

rubidium

strontium

yttrium

zirconium

niobiuim

Cs

Ba

La

Hf

Ta

cesium

barium

lanthanum

hafnium

tantalum

Names of metallic elements you should

know (continued):
Cr
chromium

Mo

Mn
manganese

Tc

Fe

Co

Ni

Cu

iron

cobalt

nickel

copper

Ru

Rh

Pd

Ag

molybdenum technetium ruthenium

W
tungsten

palladium

silver

zinc

Cd
cadmium

Re

Os

Ir

Pt

Au

Hg

rhenium

osmium

iridium

platinum gold

mercury

Lanthanides:
La
Ce
lanthanum

cerium

Actinides:
Ac
Th
actinium

rhodium

Zn

thorium

Gd

. Lu

gadolinium

lutetium

Np

Pu

Am

uranium

neptunium

plutonium

americium

Geometrical Isomerism
ammonia
chloride
Pt

Pt

cis-diamminedichloro
platinum(II)

trans-diamminedichloroplatinum(II)

Geometrical isomers can exist with two identical ligands placed

next to each (cis) or at 180 to each other (trans). Again, Werners
theory could explain how two different complexes corresponding
to [(NH3)2Cl2Pt] could exist.

Cis and trans isomerism of octahedral complexes:

green
= Cl

trans-[Co(NH3)4Cl2]+
(green)

cis-[Co(NH3)4Cl2]+
(violet)

An important aspect of Werners theory was that it could explain how

two compounds of identical formula, i.e. [Co(NH3)4Cl2]Cl, could exist
as two entirely different forms, which we now know to be the cis and
trans forms above.

fac (facial) and mer (meridional) geometrical

isomers of the [Co(NH3)3Cl3] complex

mer
mer-[Co(NH3)Cl3]

fac
fac-[Co(NH3)Cl3]

Optical isomerism:
mirror plane

(lambda) form

(delta) form

The tris(ethylenediamine)cobalt(III) complex exists as optical isomers.

the and forms, which are non-superimposable mirror images of
each other. This will be discussed further under group theory.