Transition metals and orbitals overlap

Molecular orbitals of transition metal complexes
Yves Jean
Oxford, UK; Oxford University Press | ISBN 0198530935 | 2005 | 275pp | ?39.95
Reviewed by Malcolm Halcrow

The most important single influence on the shape, spectroscopy and reactivity of a transition metal compound is the distribution of electrons within its frontier d-orbitals. This book explains these phenomena, by deriving and applying the frontier molecular orbitals of transition metal complexes from orbital overlap and symmetry arguments. Its pedagogical and qualitative approach avoids equations but uses character tables where appropriate. As an aid to the latter, a condensed introduction to group theory is also provided.

The book can be split almost evenly into two halves. First, d-orbital splittings are derived for transition ions with a wide range of coordination geometries and ligand types. 

These arguments are then expanded to show how orbital effects control the conformations and reactions of organometallic and coordination compounds. Electrostatic (crystal field) and steric effects are largely ignored during these discussions. Curiously, so is the Jahn-Teller effect.

The book is a translation from French, which has resulted in a few oddities in terminology. One that takes getting used to is the abbreviation of molecular orbital in its singular and plural forms as MO (rather than MOs). There is a modest smattering of typos and a few more serious errors. For example, the existence of high-spin and low-spin structures is not limited to d4, d5 and d6 complexes in an octahedral geometry; d7 compounds can show them as well.

The book is aimed at students and is laid out like the successful Oxford University Press primer series of undergraduate texts. It is a useful reference book for an academic transition metal chemist and it would be a good library purchase. 

However, since d-block chemistry is usually taught in UK universities starting from crystal field theory, rather than by this kind of angular overlap approach, it may not find much use as a student textbook.