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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Hydroalumination and hydrogallation reactions with tri(ethynyl)silanes - Generation of compounds with up to three coordinatively unsaturated aluminium atoms
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Hydroalumination and hydrogallation reactions with tri(ethynyl)silanes - Generation of compounds with up to three coordinatively unsaturated aluminium atoms

机译：三（乙炔基）硅烷的加氢铝化和加氢镓化反应-生成最多三个配位不饱和铝原子的化合物

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摘要

Hydroalumination or hydrogallation of tri(ethynyl)silanes, RSi(C≡C-Ar)_3 (1a, R = Ph, Ar = Ph; 1b, R = Me, Ar = Ph; 1c, R = Me, Ar = C_6H_4Me), with the element hydrides H-EtBu 2 (E = Al, Ga) in stoichiometric ratios of 1:1 to 1:3 at ambient temperature yielded the addition products (PhC≡C)_2(R) Si[(tBu_2E)C=C(H)Ph] (2, R = Ph, E = Ga; 3a, R = Me, E = Al; 3b, R = Me, E = Ga), (PhC≡C)(Me)Si[(tBu_2E)C=C(H)Ph]_2 (4a, E = Al, 4b, E = Ga) and (Me)Si[(tBu_2Al)C=C(H)Ar]_3 (5, Ar = Ph; 6, Ar = C_6H_4Me). Compounds 2-4 show a relatively close interaction between the coordinatively unsaturated aluminium or gallium atoms and one of the C~α(≡C) atoms of unreacted alkyne substituents [245 (E = Al) and 266 pm (E = Ga)] that stabilises the kinetically favoured cis addition products with E and hydrogen on the same side of the resulting C=C double bonds. In the absence of these stabilising effects the compounds were found to isomerise to the thermodynamically favoured trans isomers.
机译：三（乙炔基）硅烷RSi（C≡C-Ar）_3（1a，R = Ph，Ar = Ph; 1b，R = Me，Ar = Ph; 1c，R = Me，Ar = C_6H_4Me）的加氢铝化或加氢镓化，在环境温度下，化学计量比为1：1至1：3的元素氢化物H-EtBu 2（E = Al，Ga）产生加成产物（PhC≡C）_2（R）Si [（tBu_2E）C = C（H）Ph]（2，R = Ph，E = Ga; 3a，R = Me，E = Al; 3b，R = Me，E = Ga），（PhC≡C）（Me）Si [（tBu_2E ）C = C（H）Ph] _2（4a，E = Al，4b，E = Ga）和（Me）Si [（tBu_2Al）C = C（H）Ar] _3（5，Ar = Ph; 6， Ar = C_6H_4Me）。化合物2-4在配位不饱和的铝或镓原子与未反应的炔烃取代基的C〜α（≡C）原子之一[245（E = Al）和266 pm（E = Ga）]之间具有相对紧密的相互作用，在所得C = C双键的同一侧用E和氢稳定动力学上有利的顺式加成产物。在没有这些稳定作用的情况下，发现该化合物异构化为热力学上有利的反式异构体。

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