Photoinduced One-Pot Synthesis of a Chromium Germylyne Complex and Its Formation Mechanism

Abstract

A chromium germylyne (or germylidyne) complex having a Cr≡Ge triple bond, [Cp*(OC)2Cr≡GeTsi] (1) (Tsi = C(SiMe3)3), was directly synthesized by the photochemical reaction of a methyl chromium complex [Cp*Cr(CO)3Me] and a trihydrogermane (TsiGeH3). Detailed monitoring the reaction by NMR revealed the initial formation of hydrido (hydrogermylene) complex [Cp*(OC)2(H)Cr═Ge(H)Tsi] (2) as an intermediate and its facile release of dihydrogen to afford 1 under UV–vis light irradiation. The intermediate 2 was isolated from another experiment under blue LED light irradiation. The structures of 1 and 2 were confirmed by X-ray crystallography. Based on the analysis of absorption bands of intermediate 2 using TD-DFT calculations, we suggest possible mechanisms for releasing dihydrogen from 2 to afford 1, which includes a process forming a metallogermylene by weakening the Cr–Ge multiple bond.