CHEM F343

Coordination Chemistry:
An overview
CFT:Splitting of d-orbital energy levels in ligand fields of different symmetries
Sigma MO Diagram of Octahedral Complex
 Sigma MO Diagram of Octahedral Complex
Octahedral Point Group
Sigma MO Diagram of Octahedral Complex

t1u*

4p (t1u) a1g*

4s (a1g)
eg *

O
3d (eg + t2g)
t2g

(a1g + t1u + eg)

eg

TM 6L
t1u

a1g
 The 6 metal AO’s of proper
symmetry combine with the six
ligand group orbitals t1u*

 6 bonding MO’s are filled by ligand 4p (t1u)

a1g*

electron pairs
4s (a1g)

eg *
 The metal t2g Atomic Orbitals are
nonbonding (dxy, dxz, dyz) O

3d (eg + t2g)
t2g
 6 antibonding orbitals are formed
with the same symmetries as the
(a1g + t1u + eg)
bonding orbitals eg

 The 2 eg* antibonding orbitals are TM 6L

t1u
the lowest energy antibonding
orbitals available a1g

 The d-electrons from the metal ion

will fill in the t2g and eg* MO’s
 Sigma MO Diagram of Tetrahedral Complexes:

Tetrahedral Point Group

Sigma MO Diagram of Tetrahedral Complexes:

t2*

(n+1)p (t2) a1*

(n+1)s (a1)
t2*

t t ~ 4/9 o
nd (e + t2)
e

(a1 + t2)
a1

M 4L (LGOs)
t2
• MO Theory and Square Planar Complexes
– Sigma Bonding
• Group Theory MO Description for D4h symmetry

d orbitals:
a1g (dz2); eg (dxz, dyz); b2g (dxy); b1g (dx2-y2)

p orbitals:
a2u (pz); eu (px, py)

Γσ = A1g + Eu + B1g
2) Choose dz2, dx2-y2, px, py as most
likely orbitals from metal ion

3) Three d-orbitals are not

involved in s-bonding
(dxy, dxz, dyz)

4) The s-bonding diagram is

complex because the d-orbitals
are split into three different
groups.

5) The energy difference between

the lowest 2 d-orbital groups is
called 
 t2g*

* (t2g)
eg* eg*

large
O

t2g
-acceptor ligands
increase O
TM complex with
s-bonding only t2g

[Cr(CO)6]
with -backdonation
from Cr to CO

eg* eg*
-donor ligands
decrease O
small
O

t2g*

t2g

TM complex with t2g

L
s-bonding only
TM complex with -
donation from
Ligand to Metal
[Cr(CN)6]3-

[CrF6]3-
 MO energy levels for an octahedral complex
with -acceptor ligands (e.g. [Cr(CO)6])

t1u*

4p (t1u)
a1g*

4s (a1g)
t2g*
* orbitals of CO (t2g)
eg*

large
3d (eg + t2g) O

t2g
(a1g + t1u + eg)
eg

Cr 6 CO
t1u

a1g
 Nomenclature of Coordination
Compounds: IUPAC Rules
• The cation is named before the anion
• When naming a complex:
– Ligands are named first
• alphabetical order
– Metal atom/ion is named last
• oxidation state given in Roman numerals follows in
parentheses
– Use no spaces in complex name
 Nomenclature: IUPAC Rules
• The names of anionic ligands end with the
suffix -o
– -ide suffix changed to -o
– -ite suffix changed to -ito
– -ate suffix changed to -ato
Nomenclature: IUPAC Rules

Ligand Name
bromide, Br- bromo
chloride, Cl- chloro
cyanide, CN- cyano
hydroxide, OH- hydroxo
oxide, O2- oxo
fluoride, F- fluoro
Nomenclature: IUPAC Rules

Ligand Name
carbonate, CO32- carbonato
oxalate, C2O42- oxalato
sulfate, SO42- sulfato
thiocyanate, SCN- thiocyanato
thiosulfate, S2O32- thiosulfato
Sulfite, SO32- sulfito
 Nomenclature: IUPAC Rules
• Neutral ligands are referred to by the usual
name for the molecule
– Example
• ethylenediamine
– Exceptions
• water, H2O = aqua
• ammonia, NH3 = ammine
• carbon monoxide, CO = carbonyl
 Nomenclature: IUPAC Rules
• Greek prefixes are used to indicate the number of
each type of ligand when more than one is present
in the complex
– di-, 2; tri-, 3; tetra-, 4; penta-, 5; hexa-, 6
• If the ligand name already contains a Greek prefix,
use alternate prefixes:
– bis-, 2; tris-, 3; tetrakis-,4; pentakis-, 5; hexakis-, 6
– The name of the ligand is placed in parentheses
 Nomenclature: IUPAC Rules
• If a complex is an anion, its name ends with
the -ate
– appended to name of the metal
 Nomenclature: IUPAC Rules
Transition Name if in Cationic Name if in Anionic Complex
Metal Complex
Sc Scandium Scandate
Ti titanium titanate
V vanadium vanadate
Cr chromium chromate
Mn manganese manganate
Fe iron ferrate
Co cobalt cobaltate
Ni nickel nickelate
Cu Copper cuprate
Zn Zinc zincate
 Practice
K2[Ni(CN)4]
Potassium tetracyanonickelate(II)

Na[Cr(C2O4)2(H2O)2]
Sodium diaquabis(oxalato)chromate(III)

[Ru(phen)3]Cl3
Tris(phenanthroline)ruthenium(III) chloride
 Practice
aquachlorobis(ethylenediamine)
cobalt(III) chloride
[Co(H2O)(Cl)(en)2]Cl2

Pentacarbonyliron(0) Fe(CO)5

Triamminechloroetheylenediaminecobalt(III)
[Co(NH3)3(Cl)(en)]2+
Coordination Chemistry: Isomerism
• Isomers
 Compounds that have the same composition but
a different arrangement of atoms
• Major Types
 Structural isomers
 Stereoisomers
26
Coordination Chemistry: Isomerism
Co N5 H15 Br Cl
 Coordination-Sphere Isomers
• Example
[Co(NH3)5Cl]Br vs. [Co(NH3)5Br]Cl

Consider precipitation

[Co(NH3)5Cl]Br(aq) + AgNO3(aq)  [Co(NH3)5Cl]NO3(aq) + AgBr(s)

[Co(NH3)5Br]Cl(aq) + AgNO3(aq)  [Co(NH3)5Br]NO3(aq) + AgCl(s)

Linkage Isomers
 Linkage Isomers

Tro, Chemistry: A Molecular

30
Approach
31
 Geometric Isomers
• geometric isomers are stereoisomers that differ
in the spatial orientation of ligands
• cis-trans
fac-mer isomerism
isomerismininoctahedral
octahedralcomplexes
square-planar
complexes
complexes
MA
MA3MA
4BB32 2B2

Tro, Chemistry: A Molecular

32
Approach
 Stereoisomers
• Optical isomers
– isomers that are nonsuperimposable mirror
images
• said to be “chiral” (handed)
• referred to as enantiomers
– A substance is “chiral” if it does not have a “plane
of symmetry”
Nonsuperimposable (enantiomers)

mirror plane

cis-[Co(en)2Cl2]+
Example 1
rotate mirror image 180°

180 °
Superimposable-not enantiomers

trans-[Co(en)2Cl2]+