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Topic 8 - Coordination Compound

The document discusses the electron configurations of transition metal ions like cobalt. While neutral cobalt has an electron configuration of [Ar] 4s2 3d7, the Co2+ and Co3+ ions have configurations of [Ar] 3d7 and [Ar] 3d6 respectively, with electrons removed from the higher energy 3d orbitals rather than the 4s orbital. Most transition metals can form multiple oxidation states that give different colored complexes. Coordination complexes form when ligands bond to a central metal ion via coordinate covalent bonds. The coordination number and geometry of complexes depends on the number of ligands bonded to the metal center.

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64 views

Topic 8 - Coordination Compound

The document discusses the electron configurations of transition metal ions like cobalt. While neutral cobalt has an electron configuration of [Ar] 4s2 3d7, the Co2+ and Co3+ ions have configurations of [Ar] 3d7 and [Ar] 3d6 respectively, with electrons removed from the higher energy 3d orbitals rather than the 4s orbital. Most transition metals can form multiple oxidation states that give different colored complexes. Coordination complexes form when ligands bond to a central metal ion via coordinate covalent bonds. The coordination number and geometry of complexes depends on the number of ligands bonded to the metal center.

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izz isalah
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© © All Rights Reserved
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Download as PPTX, PDF, TXT or read online on Scribd
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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

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