2P32 Principles of Inorganic Chemistry Dr. M.

Pilkington

Lecture 3 - Classification and Nomenclature

1. Ligand
g Classification:
Coordination Chemistry and Ligands
Monodentate Ligands
Ambidentate Ligands
Bridging Ligands Biological Applications
Multi/Polydentate Chelating Ligands

2. Naming Metal Complexes

Rodgers Chapter 2.

Theory of Coordination Chemistry

Alfred Werner (1866-1919)
1893, age 26: coordination theory
Nobel prize for Chemistry, 1913
Addition of 6 mol NH3 to CoCl3(aq)

Coordination compound/complex.

NH3 3+
H
H3N NH3
N M Co
H3N 3Cl (counter ion)
H NH3
H
NH3
N forms a coordinate
covalent bond to the ligand (coordination sphere)
metal

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1. Ligand Classification

Ligand Lewis base (electron pair donor) that is bonded

to a metal ion. Ligands are anionic or neutral.

i.e. [Fe(NH3)6
]3+ N H
Metal Complex H
Ligand - Lewis Base
Fe :NH3 Has one pair of electrons

The NH3 shares its electron with the Fe(III) metal ion.
ion

Classes of Ligands

1. Monodentate Ligands

one toothed bind to a metal ion through a single

donor site.
site
For example :NH3 is a monodentate ligand.

Co3+ :NH3

Fe3+ Cl

Fe2+ C N

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2. Bridging Ligands
Bind to two or more metal ions simultaneously.
For Example: neutral ligand
2 n+
O22- (H2O)5Fe
F O F (H2O)5
Fe(H

Co3+ Cl Co3+
5+
Cl

Fe C N Fe

[(NC)5Fe(III)CNFe(III)(CN)5]5-

Fe can exist in number of oxidation states.

A biologically important metal ion.

A Biological Application of Fe
Iron-sulfur proteins are proteins characterized by the presence
of iron-sulfur clusters containing sulfide-linked iron centers in
variable oxidation states.
Structural motifs
In almost all Fe-S proteins, the Fe centers is tetrahedral and
the thiolato sulfur centers, from cysteinyl residues, are terminal
ligands. The sulfide groups are either two- or three-
coordinated. A common motif features a four iron ions and four
sulfide ions placed at the vertices of a cubane-type structure.
4Fe-4S clusters

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Aconitase - aconitate hydratase; is an enzyme that catalyses the stereo-
specific isomerization of citrate to isocitrate via cis-aconitate in the

tricarboxylic acid cycle, a non-redox-active process.

Illustration of pig aconitase in complex with the [Fe4S4] cluster. The

protein is colored by secondary structure, and iron atoms are blue and the
sulfur red.

3. Ambidentate Ligands
Two kinds of binding sites the ligand can bind one metal ion
through one or the other but not both simultaneously.
:C N: Ambidentate

Fe2+ CN It is not possible for N to bind to the same Fe2+

NO2- O N O lone pairs on O and N

can bind through either lone pair

:N C S Thiocyanide ligand can bind through S or N but not both at the

same time to one metal ion.

You will need to be able to draw the Lewis acid structures correctly so you
can figure out how a ligand will bind.

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4. Multi-/Polydentate Chelating Ligands

Multidentate multitooth; chelating - crab claw

Ligands that are bound to a metal through several donor sites.
Chelate Chelos (g
(greek)) meaning
g crab (crabs
( g
grab their food
f
with two claws, in the same way a metal can be attracted by two
lone pairs from different groups on the same ligand).
Example 1. Ethylenediamine H2NCH2CH2NH2 (en)
Forms a 5-membered chelate ring; you can think of it havings 2
claws coming in to grab the metal.
3 4
H2C CH2

H 2 H
N N
H 5 H
M
1
bidentate "two-toothed"
5-membered chelate ring

The Chelate Effect

For a given metal ion, the thermodynamic stability of a chelated

complex involving bidentate or polydentate ligands is greater
than that of a complex containing a corresponding number of
comparable monodentate ligands.

This is called the chelate effect.

5-membered rings are more stable than 6,

4 membered rings (or smaller) are not stable due to steric

4-membered
strain.

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Example 2. Ethylenediaminetetraacetate (ETDA)

O O O
O C CH2 CH2 C
O
N O
M
NCH2CH2N
N O
O CH2 CH2 O
C C
O O O
[M(EDTA)]n-
two Nitrogen's and four Oxygens bond to
a single metal ion - Hexadentate Ligand.

When we draw the ligand chelated to the metal ion we

do not draw all of the carbons.

O -
Cr
N O
Cr N
O
O O
N

[Cr(edta)]

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Examples of Multidentate Chelating Ligands
Example 3. -Diketones

R C CH2 C R' 2,4-pentadione, Ketone group on carbon
Ketone form
O
diketo O

equimolar with another form

R C CH C R' Enol form

the alcohol has an OH ending
O OH
enol

R C CH C R' the enol form can easily dissociate, i.e.

loose a H
O O

enolate anion

-Diketones bidentate ligands

e.g. R= CH3 Acetylacetone

H H
R C R' R C R'
C C
O O O O
M M

where R = CH3
acetylacetone
R R'

Ch l Ring
Chelate i
O O
M

delocalized electrons
in the double bond

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 Make sure you can draw the structures and metal complexes
of all of the ligands on your ligand sheet.

Problem Test 2007 worth 8 marks

1. Draw Lewis structures for the following ligands:

(i) Pyridine C5H5N (2 marks)

(ii) Nitrato NO3- (2 marks)

(iii) Nitro NO2- (2 marks)

Which ligand(s) above is/are ambidentate and why?

(2 marks)

2. Naming Metal Complexes refer to handout and Rodgers

textbook (pg 20-26) for rules and examples.
1. For complex ions write the cation first and anion last e.g. K2[PtCl4]
Potassiumtetrachloroplatinate.
( t you d
(note do nott use th
the prefix
fi mono, di or tri
t i etc..
t here
h to
t
indicate the number of cations)
2. Name the ligands first in alphabetical order, the metals last.
3. Prefixes to indicate numbers. (di, tri, tetra, penta, hexa etc)
for all monoatomic ligands, polyatomic ligands with short names and
neutral ligands with special names. (see Table 2.4 Rodgers).
4. Prefixes bis-, tris-, tetrakis-, pentakis-, hexakis- for ligands whose
names contain a prefix of the first type, neutral ligands without
special names, ionic ligands with particularly long names.

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For example:
[Cr(H2O)4Cl2]+ - tetraaquodichlorochromium(III) ion.
[Cr(NH2CH2CH2NH2)3]3+ - tris(ethylenediammine)chromium(III) ion.
Note the parenthesis around the organic ligand name.
5. If
f the
th anion
an on iss comp
complex,, a
add th
the suff
suffix ate
at to th
the nam
name of th
the metal.
m ta .
If the symbol comes from latin/greek, then we go back to the
latin/greek for the name of the anion.
6. Put the oxidation state in Roman numerals in parantheses after the
name of the central metal ion.
7. Practice to get the hang of this Examples from Rodgers and Practice
Handout.
For example:
[CoCl4]2- - tetrachlorocobaltate(II) ion
[Fe(CN)6]4- - hexacyanoferrate(II) ion

Ligand Names
Neutral Ligands - they have the same name as the molecule with
4 exceptions.
Molecule Name Ligand Name
NH3 Ammonia Ammine
H2O Water Aquo
CO Carbon monoxide Carbonyl
NO Nitric oxide Nitrosyl

Anionic Ligands (end in ide or e) add o

Ion Ligand Name
Cl- Chloride Chloro
OH - Hydroxide Hydroxo
SO4 2- Sulfate Sulfato

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 Naming Metal Complexes

Greek/Latin Ligand
Fe ferrum ferrate
Cu cuprum cuprate
Ag argentum argentate
Au aurum aurate
Sn stannum stannate
Pb plumbum
p plumbate
p
Hg hydrorgyrum mercurate

Bridging Ligands use to indicate a bridge.

If there is more than one of a given bridging ligand, the prefix
indicating the number of ligands is placed after the .
If there is more than one different bridging ligands, they are
given
i iin alphabetical
l h b i l order.
d
For example:
O22- peroxide
O O 3+

(H3N)4CoIII CoIII(NH3)4
NH2

amide
Tetraamminecobalt(III)--amido--peroxo-tetraamminecobalt(III) ion

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Naming Metal Complexes
Examples:
[Co(NH3)6]3+ hexaamminecobalt(III) ion.

[PtCl2(NH3)2] diamminedichloroplatinum(II)

[Fe(CN)6]4- hexacyanoferrate(II) ion.

[Fe(H2O)6]2+ hexaaquoiron(II) ion.

Problem - Test 2007

Name the compounds:
1. Na[Co(H2NCH2CH2NH2)(C2O4)ClBr] (2
marks)
2. [Zn(EDTA)]2- (2 marks)

Pay particular attention to the naming of the ambidentate

ligands

We distinguish which atom is bound to the metal in the naming

e.g. SCN- is named as thiocyanato, but NCS- is named as

isothiocyanato

CN- - cyano, but NC- - isocyano

NO2- - nitro, but ONO- is nitrito

Rodgers Chapter 2, page 22

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