Nonoctahedral structures

Acc Chem Res. 2003 Feb;36(2):147-53. doi: 10.1021/ar020052o.

Abstract

There is always a special reason when six-coordinate molecules or complexes are nonoctahedral. The Jahn-Teller distortion is the longest known example. Also well understood now is the steric activity or nonactivity of a nonbonding electron pair, for example XeF(6). In the past few years, it became obvious that six-coordinate d(0) and d(1) complexes with sigma only ligands such as Mo(CH3)(6) are far from octahedral; rather, they are trigonal prismatic or even C(3v) distorted trigonal prismatic. This phenomenon can be explained with simple molecular orbital or valence bond models.