Issue 23, 2010

Metal–dioxygen and metal–dinitrogen complexes: where are the electrons?

Abstract

Transition-metal complexes of O2 and N2 play an important role in the environment, chemical industry, and metalloenzymes. This Perspective compares and contrasts the binding modes, reduction levels, and electronic influences on the nature of the bound O2 or N2 group in these complexes. The charge distribution between the metal and the diatomic ligand is variable, and different models for describing the adducts have evolved. In some cases, single resonance structures (e.g. M–superoxide = M–O2) are accurate descriptions of the adducts. Recent studies have shown that the magnetic coupling in certain N22− complexes differs between resonance forms, and can be used to distinguish experimentally between resonance structures. On the other hand, many O2 and N2 complexes cannot be described well with a simple valence-bond model. Defining the situations where ambiguities occur is a fertile area for continued study.

Graphical abstract: Metal–dioxygen and metal–dinitrogen complexes: where are the electrons?

Article information

Article type
Perspective
Submitted
22 Jan 2010
Accepted
25 Feb 2010
First published
01 Apr 2010

Dalton Trans., 2010,39, 5415-5425

Metal–dioxygen and metal–dinitrogen complexes: where are the electrons?

P. L. Holland, Dalton Trans., 2010, 39, 5415 DOI: 10.1039/C001397H

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