Reactions of bridged rhodium and iridium hydrides with dienes and the reductive elimination of the resultant η-allylic complexes

Abstract

The rate-determining step in the formation of the η-allylic complexes [M(C₅Me₅)(all)Cl](II), obtained by reaction of [{M(C₅Me₅)}₂HCl₃](I; M = Rh, Ir) with 1,3-dienes, is cleavage of the Cl bridge in (I); the ease with which complexes (II) undergo reductive elimination (–HCl) to give [M^I(C₅Me₅)diene] depends on the positions of the substituents on the allyl ligand in (II).