Reaction Mechanisms of a Tungsten–Germylyne Complex with One or Two Molecules of Alcohols and Arylaldehydes: A DFT Study

Abstract

AbstractThe mechanisms for the reactions of a tungsten–germylyne complex with one or two molecules of alcohols and arylaldehydes have been investigated with the aid of density functional theory (DFT). The calculation results show that a germylyne complex 1a [Cp*(CO)2W≡GeC(SiH3)3] (Cp* = pentamethylcyclopentadienyl) reacts with only one molecule of alcohol to give hydrido(alkoxygermylene) complexes through coordination of the alcohol oxygen atom to the electron‐deficient germylyne germanium atom followed by hydrogen‐atom transfer from the oxygen atom to the tungsten atom, whereas 1a reacts with two molecules of arylaldehydes consecutively to lead to base‐stabilized alkoxy(germylene) complexes through C–H bond activation followed by hydrogermylation. In addition, two diastereomers can be formed from the reaction of a tungsten–germylyne complex with benzaldehyde. The interconversion of two diastereomers is involved in the consecutive decoordination of the C(O)Ph ligand, rotation of the germylene ligand, and recoordination of the C(O)Ph ligand to the germanium center. Our calculations are consistent with experimental observations and could provide new insights into the reactivity of the germylyne complex.