Hydroalumination of dialkynylgermanes—synthesis of alkenyl–alkynylgermanes with intramolecular aluminium–carbon interactions
Hydroalumination of dialkynylgermanes—synthesis of alkenyl–alkynylgermanes with intramolecular aluminium–carbon interactions
复制标题
二炔基锗烷的加氢铝化——通过分子内铝-碳相互作用合成烯基-炔基锗烷
DOI：
10.1039/c0nj00050g
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发表时间：
2010
影响因子：
3.3
通讯作者：
Jutta Kösters
中科院分区：
文献类型：
--
作者：
W. Uhl;M. Rohling;Jutta Kösters
二烷基铝锗烷R2 AlH [R = CH 2CMe 3，CMe 3，CH（SiMe 3）2]与二（苯乙炔基）锗烷R2 Ge（CC-C6 H5）2 [R = CH 3（1），C6 H5（2）]反应，通过其中一个CC三键的氢化铝化得到混合烯基-炔基锗烷R2 Ge（CC-C6 H5）[C（AlR 2）C（H）-C6 H5]（3 - 7）。在所有情况下，观察到Al和H原子在所得CC双键上的顺式排列。晶体结构测定表明，配位不饱和铝原子与完整三键中带部分负电荷的α-碳原子之间存在较强的分子内成键相互作用。这种相互作用只能通过应用非常庞大的双（三甲基甲硅烷基）甲基取代基来防止。
Reactions of dialkylaluminium hydrides, R2AlH [R = CH2CMe3, CMe3, CH(SiMe3)2], with di(phenylethynyl)germanes, R2Ge(CC–C6H5)2 [R = CH3 (1), C6H5 (2)], afforded mixed alkenyl–alkynylgermanes, R2Ge(CC–C6H5)[C(AlR2)C(H)–C6H5] (3 to 7), by hydroalumination of one of the CC triple bonds. In all cases the cis-arrangement of the Al and H atoms across the resulting CC double bond was observed. Crystal structure determinations revealed relatively strong intramolecular bonding interactions between the coordinatively-unsaturated aluminium atoms and the α-carbon atoms of the intact triple bonds bearing a partial negative charge. This interaction is only prevented by application of the very bulky bis(trimethylsilyl)methyl substituent.