Ritter Florian, Spaniol Thomas P, Douair Iskander, Maron Laurent, Okuda Jun
Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056, Aachen, Germany.
CNRS, INSA, UPS, UMR 5215, LPCNO, Université de Toulouse, 135 avenue de Rangueil, 31077, Toulouse, France.
Angew Chem Int Ed Engl. 2020 Dec 14;59(51):23335-23342. doi: 10.1002/anie.202011480. Epub 2020 Oct 15.
Protonolysis of [ZnH ] with the conjugated Brønsted acid of the bidentate diamine TMEDA (N,N,N',N'-tetramethylethane-1,2-diamine) and TEEDA (N,N,N',N'-tetraethylethane-1,2-diamine) gave the zinc hydride cation [(L )ZnH] , isolable either as the mononuclear THF adduct [(L )ZnH(thf)] [BAr ] (L =TMEDA; BAr =[B(3,5-(CF ) -C H ) ] ) or as the dimer [{(L )Zn)} (μ-H) ] [BAr ] (L =TEEDA). In contrast to [ZnH ] , the cationic zinc hydrides are thermally stable and soluble in THF. [(L )ZnH] was also shown to form di- and trinuclear adducts of the elusive neutral [(L )ZnH ]. All hydride-containing cations readily inserted CO to give the corresponding formate complexes. [(TMEDA)ZnH] [BAr ] catalyzed the hydrosilylation of CO with tertiary hydrosilanes to give stepwise formoxy silane, methyl formate, and methoxy silane. The unexpected formation of methyl formate was shown to result from the zinc-catalyzed transesterification of methoxy silane with formoxy silane, which was eventually converted into methoxy silane as well.
用双齿二胺TMEDA（N，N，N′，N′-四甲基乙烷-1，2-二胺）和TEEDA（N，N，N′，N′-四乙基乙烷-1，2-二胺）的共轭布朗斯特酸对[ZnH]进行质子解反应，得到氢化锌阳离子[(L )ZnH] ，它可以作为单核THF加合物[(L )ZnH(thf)] [BAr ] （L =TMEDA；BAr =[B(3,5-(CF ) -C H ) ] ）分离出来，也可以作为二聚体[{(L )Zn)} (μ-H) ] [BAr ] （L =TEEDA）分离出来。与[ZnH] 不同，阳离子型氢化锌热稳定且可溶于THF。[(L )ZnH] 还被证明能形成难以捉摸的中性[(L )ZnH ] 的双核和三核加合物。所有含氢化物的阳离子都能很容易地插入CO生成相应的甲酸酯配合物。[(TMEDA)ZnH] [BAr ] 催化CO与叔硅烷的硅氢化反应，逐步生成甲酰氧基硅烷、甲酸甲酯和甲氧基硅烷。结果表明，甲酸甲酯的意外形成是由锌催化甲氧基硅烷与甲酰氧基硅烷的酯交换反应导致的，最终甲酰氧基硅烷也转化为甲氧基硅烷。
