Heterobimetallic Hydrides with a Germanium(II)‐Zinc Bond

Author:

Mahawar Pritam1,Rajeshkumar Thayalan2,Maron Laurent2,Spaniol Thomas P.1,Okuda Jun1ORCID

Affiliation:

1. Institute for Inorganic Chemistry RWTH Aachen University 52056 Aachen Germany

2. CNRS INSA UPS UMR 5215 LPCNO Université de Toulouse 35 Avenue de Rangueil 31077 Toulouse France

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.

Funder

Deutsche Forschungsgemeinschaft

Publisher

Wiley

Subject

General Chemistry,Catalysis,Organic Chemistry

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