硅宾与质子氢分子的氧化加成反应合成硅氢物种
收稿日期: 2023-09-07
修回日期: 2023-10-24
网络出版日期: 2023-11-23
基金资助
国家自然科学基金(21972112); 福建省产学研(2021H6002)
Synthesis of the Hydrosilicon Species via Oxidative Addition of Silylene toward the Proton-Containing Molecules
Received date: 2023-09-07
Revised date: 2023-10-24
Online published: 2023-11-23
Supported by
National Natural Science Foundation of China(21972112); Productive Research Program of Fujian Province(2021H6002)
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-C8H14)B- (R)N]Si [L=PhC(NtBu)2; R=2,4,6-Me3C6H2 (1)、2,6-iPr2C6H3 (2)、1-C10H15 (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-C8H14)B(R)N]Si(H)[O-cyclo-CH(CH2)2N(CHPh2)] (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-C8H14)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-C8H14)B(2,4,6-Me3C6H2)N]Si(H)(NPh2) (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.
孔德亮 , 杨萧昂 , 赵怡玲 , 彭彦博 , 朱红平 . 硅宾与质子氢分子的氧化加成反应合成硅氢物种[J]. 有机化学, 2024 , 44(4) : 1311 -1318 . DOI: 10.6023/cjoc202309007
The oxidative addition reaction of silylenes with proton-containing molecules is an effective method for synthesis of hydrosilicon species. Herein, amidinatoborylaminosilylenes (L)[(1,5-C8H14)B(R)N]Si [L=PhC(NtBu)2; R=2,4,6-Me3C6H2 (1), 2,6-iPr2C6H3 (2), 1-C10H15 (3)] were employed, each of which reacted with 1-(diphenylmethyl)-3-hydroxyazetidine to produce the derived alkoxyl hydrosilicon compounds (L)[(1,5-C8H14)B(R)N]Si(H)[O-cyclo-CH(CH2)2N(CHPh2)] (4~6), and with mercaptans as 2-naphthalenethiol, 4-fluorothiophenol, 2-chlorobenzenethiol to yield thiol hydrosilicon compounds (L)- [(1,5-C8H14)B(R)N]Si(H)(SR') (7~14). Silylene 1 reacted with diphenylamine to give (L)[(1,5-C8H14)B(2,4,6-Me3C6H2)N]- Si(H)(NPh2) (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.
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