Heterobimetallic Hydrides with a Germanium(II)‐Zinc Bond

Abstract

AbstractIn the presence of TMEDA (TMEDA=N,N,N’,N’‐tetramethylethylenediamine), zinc dihydride reacted with germanium(II) compounds (BDI−H)Ge (1) and [(BDI)Ge][B(3,5‐(CF3)2C6H3)4] (3) (BDI‐H = HC{(C=CH2)(CMe)(NAr)2}, BDI = [HC(CMeNAr)2]; Ar = 2,6‐iPr2C6H3) by formal insertion of the germanium(II) center into the Zn−H bond of polymeric [ZnH2]n to give neutral and cationic zincagermane with a H−Ge‐Zn−H core [(BDI−H)Ge(H)‐(H)Zn(tmeda)] (2) and [(BDI)Ge(H)‐(H)Zn(tmeda)][B(3,5‐(CF3)2C6H3)4] (4), respectively. Compound 2 eliminated [ZnH2] giving diamido germylene 1 at 60 °C. Compound 2 and deuterated analogue 2‐d2 exchanged with [ZnH2]n and [ZnD2]n in the presence of TMEDA to give a mixture of 2 and 2‐d2. Compounds 2 and 4 reacted with carbon dioxide (1 bar) at room temperature to form zincagermane diformate [(BDI−H)Ge(OCHO)‐(OCHO)Zn(tmeda)] (5) and formate bridged digermylene [({BDI}Ge)2(μ‐OCHO)]+[B(C6H3(CF3)2)4] (6) along with zinc formate [(tmeda)Zn(μ‐OCHO)3Zn(tmeda)][B(C6H3(CF3)2)4] (7), respectively. The hydridic nature of the Ge−H and Zn−H bonds in 2 and 4 was probed by reactions with Brönsted and Lewis acids.