In 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-(CF ) C H ) ] (3) (BDI-H = HC{(C=CH )(CMe)(NAr) }, BDI = [HC(CMeNAr) ]; Ar = 2,6- Pr C H ) by formal insertion of the germanium(II) center into the Zn-H bond of polymeric [ZnH ] 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-(CF ) C H ) ] (4), respectively. Compound 2 eliminated [ZnH ] giving diamido germylene 1 at 60 °C. Compound 2 and deuterated analogue 2-d exchanged with [ZnH ] and [ZnD ] in the presence of TMEDA to give a mixture of 2 and 2-d . 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) (μ-OCHO)] [B(C H (CF ) ) ] (6) along with zinc formate [(tmeda)Zn(μ-OCHO) Zn(tmeda)][B(C H (CF ) ) ] (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.
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