Chemistry of

Coordination Compounds
Brown, LeMay Ch 24
AP Chemistry
Monta Vista High School
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24.1: Structure of Complexes
Complex: species in which a central metal ion
(usually a transition metal) is bonded to a group of
surrounding molecules or ions


Coordination compound: compound that contains
a complex ion or ions.
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A coordination compound, or complex, consists of:
Metal ion
Acts as a Lewis acid (e
-
pair acceptor)
Electrophile: species that is e
-
poor and seeks e
-
(gets attacked by nucleophile)

Ligand or complexing agent: molecule or ion with a
lone pair of e
-
that bonds to a metal ion
Acts as a Lewis base (e- pair donor)
Coordinate covalent bond: metal-ligand bond
Nucleophile: species that is e
-
rich and seeks an
e
-
poor area of a molecule (seeks an electrophile)
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Lewis Structures of common ligands
NH
3
CN
-



S
2
O
3
2-
SCN
-



H
2
O (not always included in formula, however)
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Complexation reactions
Ligand usually added in excess on AP
Usually result in color changes (colors
generally originate from e
-
transitions in a
partially filled d shell)

Change properties of metal ion
Thermodynamic (DH, DS, DG)
Electrochemical (E)
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The golden-orange compound is CoCl3*6NH3
while the purple compound only has 5
ammonia molecules in the coordinated
compound. As shown in the ball-and-stick
model, the chlorides serve as counter ions to
the cobalt/ammonia coordiation complex in
the orange compound, while one of the
ammonia molecules is replaced by Cl in the
purple compound. In both cases, the
coordination geometry is octahedral around
Co.
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Notation
Write complexes in square brackets, with charge on outside
Ex: Cu
2+
(aq) + 4 NH
3
(aq) [Cu(NH
3
)
4
]
2+
(aq)
H
|
Cu
2+
(aq) + 4 :N H (aq) Cu
|
H
:
N
H
3
2+
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Coordination number
Number of positions where a ligand can bond.
Similar to oxidation state
Each metal ion has a characteristic (i.e., typical)
coordination number, which can be predicted
according to crystal field theory.
Ag
+
: coordination number = 2 (2 ligand bonding
positions); results in a linear complex
[Ag(NH
3
)
2
]
+
(aq)
H H H
| | |
Ag+ (aq) + 2 :N H (aq) H N:Ag:NH (aq)
| | |
H H H
+
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Zn
2+
& Cu
2+
: coordination number = 4; tetrahedral complex
Ex: [Zn(H
2
O)
4
]
2+
(aq)



Pt
2+
: coordination number = 4; square planar complex (d
8
e-
structure)
Ex: [Pt(CN)
4
]
2-
(aq)
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Al
3+
, Cr
3+
, and Fe
3+
: coordination number = 6;
octahedral complex
Ex: [Cr(NH
3
)
5
Cl]
2+
(aq)
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Is dependent on:
Charge of ligand:
Ni
2+
: 6 NH
3
or 4 CN
-
(since CN
-
transfers more
negative charge)



Size of ligand:
Fe
3+
: 6 F
-
or 4 Cl
-
(larger ions take up more space)
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24.2: Chelates & Polydentate ligands
http://chemlabs.uoregon.edu/GeneralResources/models/bidentate.html
Ligands with more than one bonding position
Ethylenediamine (en, C
2
H
4
N
2
), or oxalate, C
2
O
4
2-

Ex: Cr
3+
(aq) + 3 C
2
O
4
2-
(aq) [Cr(C
2
O
4
)
3
]
3-
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24.3: Nomenclature
1. Name cation before anion; one or both may be a
complex. (Follow standard nomenclature for non-
complexes.)

2. Within each complex (neutral or ion), name all
ligands before the metal.
Name ligands in alphabetical order
If more than one of the same ligand is present, use a
numerical prefix: di, tri, tetra, penta, hexa,
Ignore numerical prefixes when alphabetizing.
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Neutral ligands: use the name of the molecule (with
some exceptions)
NH
3
ammine- H
2
O aqua-

Anionic ligand: use suffix o
Br
-
bromo- CN
-
cyano-
Cl
-
chloro- OH
-
hydroxo-

3. If the complex is an anion, use ate suffix
Record the oxidation number of the metal in parentheses
(if appropriate).
Ex: [Co(NH
3
)
5
Cl]Cl
2
pentamminechlorocobalt (III) chloride
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Nomenclature practice
1. K
4
[Fe(CN)
6
]


2. [Cr(NH
3
)
4
(H
2
O)CN]Cl
2



3. Na[Al(OH)
4
]
potassium hexacyanoferrate (II)


tetrammineaquacyanochromium
(III) chloride
sodium tetrahydroxoaluminate
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* 24.5: Color & Magnetism
Atoms or ions with a partially filled d-shell
usually exhibit color because the e
-
transitions
fall within the visible part of the EM spectrum.
Ex: transition metals such as Cu
2+
(blue) and Fe
3+

(orange)

Therefore, those with empty or filled d-shells
are usually colorless.
Ex: alkali & alkaline earth halides, Al
3+

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* 24.6: Crystal Field Theory
Created to explain why transition metal ions in complexes
(having unfilled d-shells) are not necessarily paramagnetic.

With coordination bonding, valence d-orbitals are not truly
degenerate. Instead, they split.
Some are lower in energy (more stable) and some higher.
http://scienceworld.wolfram.com/chemistry/CrystalFieldTheory.html
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The gap between the higher and lower energy levels is called
the crystal-field splitting energy, which varies with each
ligand, yielding different E, (different l, different colors).
e- in an unfilled d-shell can actually be all paired (i.e.,
diamagnetic).
Ex: Co
3+
(has 6 d e-)