Complete Hydrogen Transfer: Tin Hydride Reactivity toward Adamantylisonitrile and Benzonitrile
Complete Hydrogen Transfer: Tin Hydride Reactivity toward Adamantylisonitrile and Benzonitrile
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DOI：
10.1021/acs.organomet.8b00207
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发表时间：
2018-06-11
期刊：
影响因子：
2.8
通讯作者：
Wesemann, Lars
中科院分区：
文献类型：
--
作者：
Aicher, Frederik S. W.;Eichele, Klaus;Wesemann, Lars
金刚烷基异腈和苄腈与大体积取代的有机锡三氢化物[Ar* SnH 3] [Ar* =（C6 H 3 - 2，6-Trip（2）），Trip = 2，4，6-三异丙基苯基]反应。它们在室温和80 ℃下都不显示任何反应。在异腈的情况下，用二乙基甲胺活化有机锡三氢化物后，三个氢原子从锡原子转移到异腈单元，并形成碳锡键，得到二有机锡烯和二烷基胺之间的分子内加合物。苯甲腈和金刚烷基异腈都与低价有机锡氢化物[Ar*SnH]反应（2）。苯甲腈与低价有机锡氢化物发生插入反应，生成二聚插入产物，而金刚烷基异腈的异腈碳原子从低价有机锡氢化物中提取三个氢原子，得到（金刚烷基甲基氨基）有机锡烯和双（异腈）二锡烷加合物之间的等摩尔混合物。
Adamantylisonitrile and benzonitrile were reacted with bulky substituted organotin trihydride [Ar*SnH3] [Ar* = (C6H3-2,6-Trip(2)), Trip = 2,4,6-triisopropylphenyl]. They do not show any reaction at room temperature as well as at 80 degrees C. After activation of the organotin trihydride with diethylmethylamine in the isonitrile case three hydrogen atoms were transferred from the tin atom to the isonitrile unit and a carbon tin bond was formed to give an intramolecular adduct between a diorganostannylene and a dialkylamine. Benzonitrile as well as adamantylisonitrile react both with low-valent organotin hydride [Ar*SnH](2). Benzonitrile shows an insertion reaction with the low-valent organotin hydride to yield a dimeric insertion product, whereas the isonitrile carbon atom of adamantylisonitrile abstracts three hydrogen atoms from the low-valent organotin hydride to give an equimolar mixture between (adamantylmethylamido)organostannylene and a bis(isonitrile)distannyne adduct.