硅宾与质子氢分子的氧化加成反应合成硅氢物种  

Synthesis of the Hydrosilicon Species via Oxidative Addition of Silylene toward the Proton-Containing Molecules

作　　者：孔德亮 杨萧昂 赵怡玲 彭彦博 朱红平[1] Kong Deliang;Yang Xiaoang;Zhao Yiling;Peng Yanbo;Zhu Hongping(State Key Laboratory of Physical Chemistry of Solid Surfaces,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005)

机构地区：[1]厦门大学化学化工学院固体表面物理化学国家重点实验室,厦门361005

出　　处：《有机化学》2024年第4期1311-1318,共8页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21972112);福建省产学研(No.2021H6002)资助项目。

摘　　要：硅宾与质子氢分子的氧化加成反应是合成硅氢物种的一种有效方法.使用脒基硼胺基硅宾(L)[(1,5-C_(8)H_(14))B-(R)N]Si[L=PhC(NtBu)_(2);R=2,4,6-Me_(3)C_(6)H_(2)(1)、2,6-iPr_(2)C_(6)H_(3)(2)、1-C_(10)H_(15)(3)],分别与N-二苯甲基氮杂环丁烷-3-醇反应生成脒基硼胺基烷氧基硅氢(L)[(1,5-C_(8)H_(14))B(R)N]Si(H)[O-cyclo-CH(CH_(2))_(2)N(CHPh_(2))](4~6);与硫醇(2-萘硫醇、对氟苯硫醇、邻氯苯硫醇)反应生成脒基硼胺基芳巯基硅氢(L)[(1,5-C_(8)H_(14))B(R)N]Si(H)(SR')(7~14).硅宾1与二苯胺反应生成脒基硼胺基胺基硅氢(L)[(1,5-C_(8)H_(14))B(2,4,6-Me_(3)C_(6)H_(2))N]Si(H)(NPh_(2))(15).化合物4~15都进行了核磁共振波谱和元素分析表征,其中化合物5、7和11进行了X射线单晶衍射结构的测定.化合物4~15都是结构和组成新颖的硅氢物种,硅中心键联四个不同的基团,经由硅宾Si:中心分别对质子氢分子的O—H、S—H、N—H键的氧化加成反应生成,其中质子氢发生极性反转,形成键联于硅中心的负氢基.The oxidative addition reaction of silylenes with proton-containing molecules is an effective method for synthesis of hydrosilicon species.Herein,amidinatoborylaminosilylenes(L)[(1,5-C_(8)H_(14))B(R)N]Si[L=PhC(NtBu)_(2);R=2,4,6-Me_(3)C_(6)H_(2)(1),2,6-iPr_(2)C_(6)H_(3)(2),1-C_(10)H_(15)(3)]were employed,each of which reacted with 1-(diphenylmethyl)-3-hydroxyazetidine to produce the derived alkoxyl hydrosilicon compounds(L)[(1,5-C_(8)H_(14))B(R)N]Si(H)[O-cyclo-CH(CH_(2))_(2)N(CHPh_(2))](4~6),and with mercaptans as 2-naphthalenethiol,4-fluorothiophenol,2-chlorobenzenethiol to yield thiol hydrosilicon compounds(L)-[(1,5-C_(8)H_(14))B(R)N]Si(H)(SR')(7~14).Silylene 1 reacted with diphenylamine to give(L)[(1,5-C_(8)H_(14))B(2,4,6-Me_(3)C_(6)H_(2))N]-Si(H)(NPh_(2))(15).Compounds 4~15 have been characterized by NMR spectra and elemental analysis,of which 5,7 and 11 were further confirmed by X-ray crystallography.Compounds 4~15 are the hydrosilicon species with novel structures and compositions,all of which are bonded by four different groups,being generated by the oxidative addition reaction via the silylene Si:center toward the respective O—H,S—H,and N—H bonds of the proton-containing molecules,where a mode of a charge reversal of the proton into the hydride group at the Si center is realized.

关 键 词：硅宾 质子氢分子 氧化加成反应 硅氢化合物 

分 类 号：O627.41[理学—有机化学]