Periodic Table

The Electron Configuration of

Transition-Metal Ions
The relationship between the electron
configurations of transition metal elements
and their ions is complex.
e.g: Cobalt -two oxidation number
Co2+
Co3+
The electron configuration of a neutral cobalt
atom
Co : [Ar] 4s2 3d7
The discussion of the relative energies of the
atomic orbitals suggests that the 4s orbital has a
lower energy than the 3d orbitals.

We might expect cobalt to lose electrons from the

higher energy 3d orbitals, but this is not what is
observed.

Co2+ and Co3+ ions - electron configurations.

Co2+: [Ar] 3d7
Co3+: [Ar] 3d6
Aufbau principle
 Oxidation States of the
Transition Metal

Most transition metals form more than one

oxidation state.
Different oxidation state – different color
complex
e.g:
Fe2+ -oxidation state +2 (FeCl2-green)
Fe3+ - oxidation state +3 (FeCl3-yellow brown)
 Coordination Complex
 A coordination complex is the product of a
Lewis acid-base reaction in which ligands
bond to a central metal atom (or ion) by
coordinate covalent bonds.

Ligands are Lewis bases - contain at least one

pair of electrons to donate to a metal
atom/ion.
Coordination Complexes

Metal atoms/ions (Lewis acids) -

they can accept pairs of
electrons from Lewis bases.

A ligand - atom that is directly

bonded to the metal atom/ion is
also called the donor atom.
 Example
Co3+ +6NH3 [Co(NH3)6]3+

Electron-pair Electron-pair Acid-base

acceptor donor complex
(Lewis acid) (Lewis base)
 Covalent Bond in Coordination
Complexes

A coordinate covalent bond is a covalent

bond in which one atom (the donor atom)
supplies both electrons.

This type of bonding is different from a

normal covalent bond in which each atom
supplies one electron.
 Coordination Complexes
Coordinate bond:
H H H +
Ag+ + 2N H H N Ag N H
H H H

Coordination sphere – is the central metal and

surrounding ligands.
The square brackets separate the complex
from counter ions such as SO42-.
[Ag(NH3)2]2 SO4
-Many coordination compounds are brightly
colored.
-Different coordination compounds from the
same metal and ligands can give quite different
numbers of ions when they dissolve.
 Ligands
A ligand is a molecule, atom or ion that is
bonded directly to a metal
center by donating a pair of electron

Metal ion Ligan

d
[Ag(NH3)2]NO3
 Anionic ligands (-ve charge)

F- OH- H-
CO3 2-

Cl- [CH3O]- C6H5-

[CNO]-
Br- CN- [NO3]- C5H5-
I- HSO3- [NO2]- N3-
N3-
O2- O2- [SO3]-
[NH2]-
O22-
Neutral ligands Cationic ligands-
+ve charge
H2 O
NH3
CO
NH2NH3+
NO
C2H4
CH3NH2
2HNCH2CH2NH2
py
phen
bipy
PPh3
 Monodentate ligand
-Monodentate ligands -Lewis bases that donate a
single pair ("mono") of electrons to a metal atom
and occupy only one coordination site.
-Monodentate ligands can be either ions (usually
anions) or neutral molecules.

e.g:
 Bidentate ligand
-Bidentate ligands are Lewis bases that donate
two pairs ("bi") of electrons to a metal atom
and occupy two coordination sites

e.g:
 Polydentate ligand

Polydentate ligands (also called

multidentate ligands) have more than one
point of attachment to the metal center
and occupy more than one coordination
site.
e.g:
Ligand
Oxidation State -Possitive Complex

[Mn(H2O)6]Cl2

[Mn(H2O)6]2+ 2Cl-

Oxidation state of Mn : H2O – ligand neutral

x + 6(0) = +2
x = +2

Writing : Mn2+ manganese(II)

Oxidation State -Negative Complex
K2[PtCl4]

2 K+ [ PtCl4]2-

Oxidation state of Pt : Cl- -ligand -ve

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

Writing : Pt2+
Platinate(II)
 Charge and Oxidation State
Charge of the complex is the sum charges on
the central metal and ligands
e.g:

[Cr(H2O)4Cl2] [Cu(NH ) ]2+

+ve – positive complex
3 4

0 – neutral complex
Coordination Numbers
and Geometry
Coordination Number (CN)
CN=4

The atom that supplies

the lone pairs of
electrons for the metal-
ligand bond is the
CN=6
donor atom.
The number of these
atoms is the
coordination number.
 CN=1 and Geometry

CN= 1
Rare
e.g: Metal Cu(I) and Ag(I)

Cu(2,4,6-Ph3C6H2)
 CN=2 and Geometry

CN= 2
Also rare geometry – Linear
e.g: [ Ag(NH3)2 ]+ , [Hg(CN)2] , [CuCl2]-

with d0

Linear complex
 CN=3 and Geometry
CN=3
First row transition metal ions
e.g: 3 different geometries
e.g:
Triphenylphosphine – PPh3
Di(trimethylsily)amide – N(SiMe3)2

e.g: Complexes

[ Au(PPh3)3]+ & [Cu(PPh3)3]

 CN=4 and Geometry
 CN=4

Tetrahedral & Square planar

SF4 & TeCl4 MnO4- & CrO42-

 CN=5 and Geometry
 CN=5

Structure possible

trigonal bipyramid

Square pyramid pentagonal plane

e.g : Fe(CO)5 & [CuCl5]3-

 CN=6 and Geometry
 CN=6

Octahedral
 Structure

some trigonal prismatic

e.g: [Co(en)3]3+ & [Co(NO2)6]3-

Examples
 CN=7 and Geometry
 CN=7
All shape are found experimental

Structure pentagonal bipyramid

capped trigonal capped octahedron

e.g: [NiF7]2- & [ NbF7]2-

Examples
 CN=8 and Geometry
 CN=8

Exists only in simple lattices

square antiprism
Structure
dodecahedron
Example
 CN= 9 and Geometry
 CN=9

Structure tricapped trigonal prismatic

e.g: [ Sc(H2O)9]3+ & [Y(H2O)9]3+

 CN> 9 and Geometry
 CN
>9
Generally confined to f block metal ions

e.g: cubeoctahedral arrangment