Abstract
Publisher Summary The construction of models of molecular geometry has been a popular exercise for many years. In the field of main-group stereochemistry the ideas of Sidgwick, Powell, Nyholm, and Gillespie have been successfully fused together into the VSEPR scheme, where the electron pairs around a central atom adopt the minimum energy consistent with their mutual electrostatic repulsion. The VSEPR rules have captured much of the essence of main-group stereochemistry and are unrivalled in their simplicity. In addition, Walsh diagrams quantified by the work of Gimarc and others, and the pseudo Jahn-Teller formalism introduced by Bartell (9) into the structural field and extended by Pearson (10, 11) have provided a molecular orbital interpretation of the wide range of available structural data. By way of contrast, fewer gas-phase structures of transition metal complexes are known: a few d0–d4 hexafluorides (all octahedral), do–d1 tetrachlorides (tetrahedral), and some 18-electron carbonyl and phosphine structures typified by tetrahedral Ni(CO)4 octahedral Cr(CO)6, and trigonal bipyramidal Fe(CO)5.
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