Reversibility in free-radical reactions of aryltellurides with tributylstannyl, tributylgermyl and tris(trimethylsilyl)silyl radicals
作者:Carl H. Schiesser、Melissa A. Skidmore
DOI:10.1016/s0022-328x(97)00491-9
日期:1998.2
spectroscopies reveal that methyl, primary and secondary alkyl radicals, generated through the reaction of aryltelluroalkanes (4–9) with tributyltin hydride, tributylgermanium hydride or tris(trimethylsilyl)silane) under standard radical conditions (benzene, AIBN) are capable of displacing tributylstannyl, tributylgermyl and tris(trimethylsilyl)silyl radicals from aryltellurotributylstannanes (1, 2), aryltellurotributylgermanes
1个H,13 C,29的Si,77硒,119 Sn和125个碲NMR波谱表明,甲基,伯和仲烷基,通过aryltelluroalkanes(的反应所产生的4 - 9)与三丁基锡氢化物,tributylgermanium氢化物或三(三甲基甲硅烷基)硅烷)标准自由基条件(苯,AIBN)下是能够置换三丁基锡烷基,tributylgermyl和三(三甲基硅基)从aryltellurotributylstannanes(甲硅烷基的1,2),aryltellurotributylgermanes(10,11)和aryltellurotris(三甲硅基)硅烷(13,14)。这些观察结果与高级从头算分子轨道研究一致。使用(化合价)双计算ζ补充有偏振功能,并与包含电子相关(MP2 / DZP)的赝基组预测甲锡烷基的位移(SNH能量壁垒3),甲锗烷基烷(GeH 3)和trisilylsilyl(( ħ 3 Si