Transition Metal Complexation of σ Bonds

Abstract

Abstract The first σ complexes were found in the 1960s and 1970s, but they did not attract more than passing attention. Only now are we beginning to recognize their key role in the chemical reactions of σ bonds, and this has encouraged more detailed study. In contrast with the more familiar π‐donor complexes such as M(CH 2 CH 2 ) and complexes like MNH 3 , in which the one pair of electrons on the N atom is bound to the metal atom, in a σ complex an XH group binds to the transition metal atom; the XH σ‐bonding electron pair acts as a 2e donor to give an (X‐H)‐M type complex. Dihydrogen complexes (X = H) are one important group of σ complexes. C‐H‐M complexes (X = R 3 C) with an agostic C‐H‐M interaction have not only been found in the ground state but also implicated in the transition states of many important organometallic transformations such as Ziegler–Natta catalysis and sigma bond metathesis. The importance of XH bond activation will encourage continued growth in this field.