Coordination Chemistry

Contents
I Introduction
1 History
2 Definition
3 Nomenclature
II Bonding
1 VBT & Crystal Field Theory
2 MOT & Ligand Field Theory
3 Electronic Spectroscopy
4 Magnetic Properties
III Structure of Coordination Compounds
IV Reactivity & Reaction Mechanisms
V Descriptive Chemistry
I Introduction
1 History
1827 Discovery of Zeises Salt (KPtCl3C2H4)
The war between Alfred Werner & Sophus Jrgensen
an experimentalist versus an experimentalist seeking for insight
Complex Color old name IUPAC name
CoCl36NH3 yellow Luteo complex hexaamminecobalt(III)
chloride
CoCl35NH3 purple Purpureo complex pentaamminechlorocobalt(III)
chloride
CoCl34NH3 green Praseo complex trans-tetraamminedichlorocobalt(III)
chloride
CoCl34NH3 violet Violeo complex cis-tetraamminedichlorocobalt(III)
chloride
Jrgensen Stick on the idea of valence
Co(NH3NH3Cl)3
Cl2Co(NH3NH3NH3NH3NH3Cl)
ClCo(NH3NH3Cl)2
Cl2Co(NH3NH3NH3NH3Cl)
By considering both precipitation of AgCl and conductivity (Table
11.1): Werner proposed:
[Co(NH3)6]Cl3
[Co(NH3)5Cl]Cl2
[Co(NH3)4Cl2]Cl
[Co(NH3)4Cl2]Cl
primary valence (formal oxidation state)
secondary valence (coordination number)
Werners experiments for the conductivity of some coordination
complexes

2 Definition
A coordination compound is consisted of two components:
the metal ion (atom) and the ligand(s).
A ligand is an ion, a molecule, or a group that is associated
with the metal ion as a Lewis acid-base adduct.
The donor atom is the atom in the ligand, that attaches to
the metal ion.
A ligand has only one donor atom is a monodentate; with
two donor atoms will be bidentate; tridentate for three;
tetradentate for four..etc.
A ligand that has more than one donor atom is of multi-
dentate.
The association mold of a multidentate is called chelation.
A bridging ligand attaches to more than one metal ion.
 Isomerism and Structural insight
Structural Isomers
Hydrate Isomers
[Co(NH3)4(H2O)Cl]Cl2 and [Co(NH3)4(Cl2)]ClH2O
Ionization Isomers
[Co(NH3)5(SO4)](NO3) and [Co(NH3)4(NO3)](SO4)
Coordination Isomers
[Co(en)3][Cr(CN)6] and [Co(CN)6][Cr(en)3]
Linkage Isomers
Pd(AsPh3)2(SCN)2 and Pd(AsPh3)2(NCS)2
[Co(NH3)5(NO2)]2+ and [Co(NH3)5(ONO)]2+
Stereoisomers
Four-Coordinate
Tetrahedral
TiCl4, CoCl42-, CuCl42-, Pt(PPh3)4,

Geometrical Isomers

Optical Isomers Lacking two perpendicular C2 symmetry

 Six-Coordinate
Geometrical Isomers
Trans and cis - forms

mer and fac - forms

For an octahedral complex that has six different ligands

 Two optical isomers

Structure versus number of isomers

Questions remained: Are isomers always synthesizable?
Optical Isomers with Bidentate Chelation
 nl - nr nl and nr are the refractive index of the left and

right circularly polarized light respectively

[], the specific rotation is defined as left; wherein c' is
c'd' the concentration and d' is the thickness of the sample

MWxis molar rotation

kl - kr kl and kr are the absorption coefficients of the left

l - r
c and right circularly polarized light respectively
Asymmetric bidentate ligands

chiral without carbon

 Tridentate

Tetradentate