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Coordination Chemistry

Coordination Compounds
Coordination compound is a neutral species containing one or
more complex ions.
Complex ion contains a central metal atom or ion bonded to
one or more ions or molecules
Werner Coordination Theory
Most elements exhibit two types of valence:
i) primary valence - corresponds to the oxidation number
ii) secondary valence - corresponds to coordination number
Example:

CoCl3.6NH3
primary valence = +3

or

[Co(NH3)6]Cl3

sec. valence or coordn # = 6

Coordination Chemistry
The formula [Co(NH3)6]Cl3 indicates that the ammonia
molecules and the cobalt atom form a complex ion; the
chloride ions are not part of the complex but are held to it
by ionic forces.
ionic

coordinate or dative
covalent bond

Ligands - the molecules or ions that surround the metal in a


complex ion.

Coordination Chemistry
The interactions between a metal atom and the ligands is kind
of Lewis acid-base reaction.
Ligand acts as Lewis base donating one or more electron
pairs to the metal, the Lewis acid.
The metal-ligand bonds are usually coordinate covalent
bonds.
Every ligand has at least one unshared pair of valence
electrons.
Examples

Coordination Chemistry
Donor atom - The atom in a ligand that is bound directly to the
metal atom.
Example:
In [Co(NH3)6]Cl3, N in NH3 is directly bound to Co; N is the
donor atom.

Coordination Chemistry
Coordination number (CN) - the number of donor atoms
surrounding the central metal atom in a complex ion.
Examples:
Ag+ in [Ag(NH3)2]+ ; CN = 2 (2 N, one from each NH3)
Cu+2 in [Cu(NH3)4]+2 ; CN = 4 (4 N, one from each NH3)
Fe+3 in [Fe(CN)6]-3 ; CN = 6 (6 C, one from each CN-)
Classification of Ligands based on the number of donor atoms
present per molecule or ion:
1. Monodentate - 1 donor atom per molecule
Examples:

Coordination Chemistry
2. Bidentate - 2 donor atoms per molecule of ligand
Example:
ethylenediammine (en)

The two nitrogen atoms can coordinate with a metal atom


as shown
Structure of metal-ethylenediamine complex.
Each ethylenediamine
molecule provides two N
donor atoms and is therefore
a bidentate ligand.
Simplified structure of
the same complex.

Coordination Chemistry
Bidentate and polydentate ligands are also called chelating
agents because of their ability to hold the metal atom like a
claw (from the Greek chele, meaning claw).
Example:
ethylenediaminetetraacetate ion (EDTA), (hexadentate)
- a polydentate ligand used to treat metal poisoning

Coordination Chemistry
Six donor atoms enable EDTA to form a very stable complex ion
with lead.
In this form it is removed from
the blood and tissues and
excreted from the body.
EDTA is also used to clean up
spills of radioactive metals.

EDTA complex of lead.

Coordination Chemistry
Oxidation Numbers (ON) of Metals in Coordination Compounds

The net charge of a coordination compound or complex ion is


the sum of the charges on the central metal atom and its
surrounding ligands.
Examples:

Let x = ON of metal

[PtCl6]-2 :

x + 6(-1) = -2 ; x = +4

[Co(NH3)4Cl2]+ :

x + 4(0) + 2(-1) = +1 ; x = +3

[Co(NH3)5Cl]Cl2 : x + 5(0) + 1(-1) +2(-1) = 0 ; x = +3


(NH4)[Ni(NH3)2(C2O4)2] : +1 + x + 2(0) +2(-2) = 0 ; x = +3

Coordination Chemistry
[Pt(NH3)4][PtCl4]2

(known OS of Pt: +2, +4)

The sum of oxidation states for a neutral compound is zero.


[Pt(?)(NH3)4] [Pt(?)Cl4 ]2
[+2+4(0)] + [+2+4(-1)]2 0

; [Pt(+2)][ Pt (+2)] is incorrect

[+4+4(0)] + [+4+4(-1)]2 0

; [Pt(+4)][ Pt (+4)] is incorrect

[+2+4(0)] + [+4+4(-1)]2 0

; [Pt(+2)][ Pt (+4)] is incorrect

[+4+4(0)] + [+2+4(-1)]2 = 0

; [Pt(+4)][ Pt (+2)] is CORRECT

Coordination Chemistry
Exercises:
Specify the oxidation number of the central metal atom in
each of the following compounds:
(a) [Ru(NH3)5(H2O)]Cl2
(b) [Cr(NH3)6](NO3)3
(c) [Fe(CO)5]
(d) K4[Fe(CN)6]

Nomenclature

Nomenclature

Nomenclature

Nomenclature

Nomenclature

Nomenclature

Nomenclature
Nomenclature Rules
1. The positive ion (cation) comes first, followed by the
negative ion (anion).
Examples: diamminesilver(1) chloride, [Ag(NH3)2]Cl
potassium hexacyanoferrate(lII), K3[Fe(CN)6]
2. Within the coordination sphere, the ligands are named
before the metal, but in formulas, the metal ion is written
first.
Examples: tetraamminecopper(II) sulfate, [Cu(NH3)4]SO4
hexaamminecobalt(III) chloride, [Co(NH3)6]Cl3

Nomenclature
3. The number of ligands of one kind is given by the following
prefixes. If the ligand name includes these prefixes or is
complicated, it is set off in parentheses and the second set
of prefixes is used.
2
3
4
5
6
7
8
9
10

di
tri
tetra
penta
hexa
hepta
octa
nona
deca

bis
tris
tetrakis
pentakis
hexakis
heptakis
octakis
nonakis
decakis

Nomenclature
Examples: dichlorobis(ethylenediamine)cobalt(III),
[Co(NH2CH2CH2NH2)2CI2]+
tris(bipyridine)iron(II), [Fe(NH4C5-C5H4N)3]2+
4. Ligands are named in alphabetical order (according to the
name of the ligand, not the prefix), although exceptions to
this rule are common. An earlier rule gave anionic ligands
first, then neutral ligands, each listed alphabetically.
Examples: tetraamminedichlorocobalt(III), [Co(NH3)4CI2]+
(tetraammine is alphabetized by a and
dichloro by c, not by the prefixes)

amminebromochloromethylamineplatinum(II),
[Pt(NH3)BrCl(CH3NH2)]

Nomenclature
5. Anionic ligands are given an o suffix. Neutral ligands retain
their usual name. Coordinated water is called aqua and
coordinated ammonia is called ammine.
Examples: chloro, Clbromo, Brsulfato, SO42-

methylamine, CH3NH2
ammine, NH3 *
aqua, H2O

*(the double m distinguishes NH3 from alkyl amines)

6. Two systems exist for designating charge or oxidation number:


a. The Stock system puts the calculated oxidation number of
the metal ion as a Roman numeral in parentheses after the
name of the metal. (commonly used)

Nomenclature
b. The Ewing-Bassett system puts the charge on the
coordination sphere in parentheses after the name of the
metal. (used by Chemical Abstracts)
In either case, if the charge is negative, the suffix -ate is added
to the name of the coordination sphere.
Examples:

[Pt(NH3)4]2+
tetraammineplatinum(II) or tetraammineplatinum(2+)

[PtCl4]2tetrachloroplatinate(II) or tetrachloroplatinate(2-)
[PtCl6]-2
hexachloroplatinate(IV) or hexachloroplatinate(2-)

Nomenclature
7. The prefixes cis- and trans- designate adjacent and opposite
geometric locations.

Examples:
cis- and trans-diamminedichloroplatinum(II), [PtCl2(NH3)2]
cis- and trans-tetraamminedichlorocobalt(III), [CoCl2(NH3)4]+

cis

trans

Nomenclature
8. Bridging ligands between two metal ions as in have the
prefix -.
Example:
-amido--hydroxobis(tetramminecobalt)(4+),
[(NH3)4Co(OH)(NH2)Co(NH3)4]4+

Nomenclature
tris(tetraammine--dihydroxocobalt)cobalt(6+) bromide
[Co(Co(NH3)4(OH2)3]Br6

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Nomenclature
9. When the complex is negatively charged, the names for the
following metals are derived from the sources of their
symbols, rather than from their English names:
iron (Fe) : ferrate
silver (Ag) : argentate
gold (Au): aurate

lead (Pb): plumbate


tin(Sn): stannate

Examples:
tetrachloroferrate(III) or tetrachloroferrate(1-), [FeCl4]dicyanoaurate(I) or dicyanoaurate(1-), [Au(CN)2]-

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Nomenclature
Exercises:
Name the following coordination complexes:
1. [Cr(NH3)3Cl3]
2. [Pt(en)Cl2]
3. [Pt(ox)2]24. [Cr(H2O)5Br]2+
5. [Cu(en)Cl4]26. [Fe(OH)4]-

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Nomenclature
Exercises:
Give the structures of the following coordination complexes:
1. Tris(acetylacetonato) iron(III)
2. Hexabromoplatinate(2-)
3. Potassium diamminetetrabromocobaltate(III)
4. Tris(ethylenediamine)copper(II) sulfate
5. Hexacarbonylmanganese(I) perchlorate
6. Ammonium tetrachlororuthenate(1-)

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