Chapter 7

d-Metal Complexes

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 Introduction
coordination compound or metal complex
• coordination sphere
• ligands
• chelate

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 Coordination Chemistry
Nomenclature
Rules for Coordination Compounds:
• neutral compound
• ionic => cation before anion

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 Ligands
Neutral Molecules
• water => aqua
• ammonia => amine
• ethylenediamine (en)
• pyridine (py)
• 1,10-phenanthroline (phen)
• 2,2'-bipyridine (bipy)
• 4,4'-bipyridine
• triphenylphosphine
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 Ligands
Anions
• F- => fluoro
• Cl- => chloro
• Br- => bromo
• I- => iodo
• O-2 => oxo
• OH- => hydroxo
• CN- => cyano
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 Ligands
Anions
• HSO3- => bisulfito
• H- => hydrido
• C6H5- => phenyl (ph)
• C5H5- => cyclopentadienyl
• CO3-2 => carbonato

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 Multiplicity
monodentate
• mono => 1
• di => 2
• tri => 3
• tetra => 4
• penta => 5
• hexa => 6
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 Multiplicity
bi- or tri- dentate
• bis => 2
• tris => 3
• tetrakis => 4

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 Special Bonding Conditions
• Bridging units => 
• Delocalized bonding => 

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 Coordination Sphere
Nomenclature
• Cationic coordination sphere
– -ium ending
Anionic coordination sphere
– -ate ending

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 Nomenclature
Neutral molecule
[Ru(NH3)4(HSO3)2]
bis(bisulfite)tetraamineruthenium(II)

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 Nomenclature
Anionic coordination sphere
K3[Fe(CN)6]
potassium hexacyanoferrate(III)

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 Nomenclature
Cationic coordination sphere
[Cu(NH3)4]SO4
tetraaminecopper(II) sulfate

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 Nomenclature
Cationic coordination sphere & Anionic
coordination sphere
[Ti(H2O)6][CoCl6]
hexaaquatitanium(III)
hexachlorocobaltate(III)

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 Position Numbering
1
|
5-----2
/M /
4-----3
|
6
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 Geometric Isomerism
• cis => 2 adjacent ligands
• trans => 2 ligands across the center of
coordination sphere

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 cis and trans
Geometric Isomerism
[PtCl2(NH3)2]

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 Geometric Isomerism
• fac (facial) => three identical ligands
occupying the corners of a common
triangular
• mer (meridional) => three identical ligands
occupying three consecutive corners of a
square plane

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 fac and mer
Geometric Isomerism
[IrH3(PPh3)3]

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Linkage Isomerism

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Ionizational Isomerism

[CoIII(NH3)5Br]SO4

[CoIII(NH3)5SO4] Br

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Coordination Isomerism

[CrIII(H2O)6][CoIIICl6]

[CoIII(H2O)6][CrIIICl6]

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Optical Isomerism

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 Werner's
Coordination Theory
1913 Nobel Prize in Chemistry
Theory of the structure of coordination
compounds

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 Werner's
Coordination Theory
• primary valence => ion charge
• secondary valence => coordination number
• inner sphere => ligands bonded directly to
metal ion
• outer sphere => next sheath of ions or
molecules

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 Werner's
Coordination Theory
[Co(NH3)6]Cl3 Oh
[Co(NH3)5Cl]Cl2 C4v
cis-[Co(NH3)4Cl2]Cl C2v
trans-[Co(NH3)4Cl2]ClD4h

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 Valence Bond
Model of Bonding
effective atomic number (EAN)
EAN = (atomic number - ion charge)
+ (total number of electrons from ligands)

Dr. S. M. Condren
 Valence Bond
Model of Bonding
effective atomic number (EAN)
EAN = (atomic number - ion charge)
+ (number of ligands * number of electrons
per ligands)

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 EXAMPLES
[Co(NH3)6]Cl3
EAN = (27 - 3) + (6 * 2) = 36
[Ru(NH3)4(HSO3)2]
EAN = (44 - 2) + (6 * 2) = 54
[Cu(phen)2 4-methyl-py](ClO4)2
EAN = (29 - 2) + (5 * 2) = 37

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d-Orbitals

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Octahedral Splitting Pattern of d-Orbitals

+6Dq

10Dq

-4Dq

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Magnetic Susceptibility

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 Magnetic Susceptibility
• Total magnetic moment is given by the Lande
equation
S(S+1) – L(L+1) + J(J+1)
M = 1 + -------------------------------- J(J+1)
 J(J+1)

 When the metal ions are surrounded by ligands

in complexes, the orbital contribution to the
magnetic moment is often quenched (L = 0 and
J = S)

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 Magnetic Susceptibility
M = n(n + 2)
where n = number of unpaired electrons

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 Magnetic Susceptibility
Octahedral complexes of NiII, n = 2
M = 2(2 + 2) = 2.82 Bohr magnetons
where n = 2

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d2 Case

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d3 Case

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d4 Strong Field – Low Spin Case

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d4 Weak Field – High Spin Case

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 d Case
3

3d 4s 4p
Cr+3
d2sp3
[Cr(NH3)6]+3

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 d Case
6

3d 4s 4p
Co+3 , Fe+3
low spin d2sp3
[Co(NH3)6]+3

[Fe(CN)6]-4

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 d Case
7

3d 4s 4p 4d
Co+2
high spin d2sp3
[Co(NH3)6]+2

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 d Case
8

3d 4s 4p 4d
Ni+2
high spin sp3d2
[Ni(NH3)6]+2

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 d Case
10

3d 4s 4p
Zn+2
sp3
[Zn(NH3)4]+2
tetrahedral

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 Spectrochemical Series
• Ligands can be arranged into a
spectrochemical series according to the
magnitude of splitting of the d-orbitals
• Large splitting is associated with strong field
ligands
• Small splitting is associated with weak field
ligands
CN-1>en>NH3>H2O>F-1>SCN-1> Cl-1> Br-1> I-1

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Ligand-field Stabilization Energy

LFSE = x(-4Dq) + y(+6Dq)

where
x = number of electrons in lower levels
y = number of electrons in upper levels

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 Ligand Field Stabilization Energy,
LFSE
d1 d2 d3

LFSE = -4Dq -8Dq -12Dq

High Spin Low Spin High Spin Low Spin

d4 d5

LFSE = -6Dq -16Dq 0Dq -20Dq

Dr. S. M. Condren
 Ligand Field Stabilization Energy,
LFSE
High Spin Low Spin High Spin Low Spin

d6 d7

LFSE = -4Dq -24Dq -8Dq -18Dq

d8 d9 d10

LFSE = -12Dq -6Dq 0Dq

Dr. S. M. Condren
 LFSE of Octahedral Complexes
Example Strong Weak
d0 Ca+2,Sc+3 0 upe- 0 Dq 0 upe- 0 Dq
d1 Ti+3 1 -4 1 -4
d2 V+3 2 -8 2 -8
d3 Cr+3, V+2 3 -12 3 -12
d4 Cr+2, Mn+3 2 -16 4 -6
d5 Mn+2, Fe+3 1 -20 5 0
d6 Fe+2, Co+3 0 -24 4 -4
d7 Co+2 1 -18 3 -8
d8 Ni+2 2 -12 2 -12
d9 Cu+2 1 -6 1 -6
d10 Cu+, Zn+2 0 0 0 0
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Octahedral Splitting Pattern of d-Orbitals


 Jahn-Teller effect

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Octahedral Splitting Pattern of d-Orbitals

O>T thus no strong field vs. weak field cases

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Octahedral Splitting Pattern of d-Orbitals

[Ni(CN)4]-2

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Ligand
Field
Theory

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 Ligand Field Splitting Energy
Ligands
Ions 6F- 6H2O 6NH3 3en 6CN-
d3 Cr+3 15.06kK 17.4kK 21.5kK 21.9kK 26.6kK
d5 Mn+2 7.75 8.5 --- 10.1 ~30
Fe+3 13.35 14.0 --- --- 35.0
d6 Co+3 13.1 20.7 22.87 23.6 32.2
Rh+3 22.6 27.2 34.1 34.6 44.9
d8 Ni+2 7.25 8.50 11.0 11.85
Italics – strong field complexes; K = cm-1

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4-Coordinate

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 5-Coordinate

trigonal distorted square

bipyramidal tetragnal pyramidal

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6-Coordinate

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7 Coordinate

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8-Coordinate

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