LIGAND FIELd theory- coordination chemistry

GAYATHRI M
ROLL NO. 21302002
MSC CHEMISTRY 1ST YEAR
NIT MANIPUR
 CONTENTS
 1) DEMERITS OF CFT


 2) LFT– INTRODUCTION
 Assumptions of MOT
 Metal orbitals
 3) SYMMETRY SYMBOLS
 4)LGO- a brief study
 5)MOT- sigma bonding in octahedral complex
 pi bonding in octahedral complex
 6)Conclusion
 Demerits of Crystal Field Theory

 1.CFT does not take care of covalent character b/w metal & ligands.
 2.could not explain bonding strength and chemical properties in several
complexes.
 3.fails to explain satisfactorily the relative strength of ligands.
 eg; can not explain why OH- is weaker ligand than neutral H2O.
 4.can not explain pi bonding in complexes.
 5.considered the role of metal ion d-orbitals only in metal ligand
interaction. Could not explain the contribution of s and p orbitals.
Experimental Evidences for metal ligand covalent bonding

 Electron spin resonance(ESR) spectra

 esr is a branch of absorption spectroscopy, in which molecules having electrons with
unpaired spins absorb radiations of microwave frequency.

 .

For hexachloroiridinium(2-) unpaired

electron 70% localized on metal and
30% is localized on chloride ion.this
indicates there is a sharing of electron

This pixelated (not-smooth) curve

indicates that this single electron
can travel from metal orbital to ligand
orbital & it’s possible only when
there is an overlap b/w ligand orbital
and metal orbital. This overlap
indicating there is a covalent bonding
b/w metal and ligand.

.
 Nephelauxetic effect
 Nephelauxetic--- cloud expanding(greek word)
 This effect explains the decrease in interelectronic repulsion of metal d –
electrons when the complex formation takes place.
 .

d d elecetron repulsion is less in

complex metal ion compaired to
the free metal ion or free metal ion.
That decrease in interelectronic
repulsion in complex metal is due to
the expansion of electron cloud & its
possible only when there is an
overlapping b/w metal and ligand
orbitals. That indicates covalent
interaction.
This effect is known as nephelauxetic
effect.
 LFT – LIGAND FIELD THEORY

Introduction

History
1) CFT only considers ionic interaction in metal complex.
2) MO theory developed & applied only to non- metal compounds.
3) LFT combines both CFT & MO for transition metal coordination
compounds.

LFT considers covalent interaction b/w the metal and ligand.

LFT uses a molecular orbital approach.

Assumptions of MOT

 1.Central metal ion contribute 9 AOs for bonding.

 2.Six orbitals used for sigma bond formation.
Metal orbitals
Symmetry symbols of metal orbitals
 Ligand group orbitals (LGO)-A brief study

 In an octahedral complex 6 equivalent ligand atoms contribute a hybrid atomic orbital to form
sigma bonds.
 6 AOs of six ligands in an octahedral complex combine together linearly to form a set of LGO.
 LGOs constructed on the basis of group theory.
 By using character table for octahedral point group, by determining reducible representation
 We can find the symmetries of LGOs.
LGOs with their symmetry matched with metal orbitals
MOT for sigma bonding in octahedral complex
MOT for pi bonding octahedral complex

 The pi bonding can be explained by LFT.

 Pi bonding will be significant if the metal & ligand orbital
have proper pi symmetry,comparable size & energy.
 The metal ligand orbitals involving in pi bonding are
perpendicular to M –L axis.
 For metal its t2g set are nonbonding so these orbitals are
involved in pi bonding.
.

 Symmetry adapted atomic orbitals for M-L sideways overlap can

be obtained resolving RR based on displacement vectors
perpendicular to the axis of sigma overlap.
 Each of 6 ligands have 2 basis-vectors for pi symmetry.
 Type of ligands

 1) pi donor ligand
 These ligands having
filled t2g LGOs.
 Lower energy than metal
t2g orbitals.
 Eg; F-,Cl-,Br-,OH-
 Decrease in crystal field
splitting parameter .
 Weak field ligands.
 Situated at the lower end
of spectrochemical
series.
 .

 2)pi acceptor ligands

 t2g ligand orbitals are empty.
 Higher energy than metal t2g orbitals.
 Eg; R3P ,R3As (vacant d orbital)
 CO,CN-,NO+ (vacant pi* orbital)
 Increase in crystal field splitting
parameter.
 Strong field ligands.
CONCLUSION

 Unlike in other theories (VBT,CFT) both covalent & ionic

contributions are fully allowed for this theory.

 The power behind any theory is how well it explains

properties,spectroscopic behavior of compounds, magnetic
behavior etc. therefor this theory advantageous in several aspects
over the previous theories.

 The best understanding of the chemistry of the metal complexes

can be obtained only by the use of LFT.
 Reference

1) Inorganic Chemistry- Coordination

- N Ajai Kumar
2) Inorganic chemistry by Catherine Housecroft,Alan G. Sharpe
3) Textbook of inorganic chemistry Vol.1
-Mandeep Dalal
ACKNOWLEDGEMENT

Dr. Mithun Roy

Assistant Professor , Department of Chemistry
NIT Manipur
Thank You!

GAYATHRI M