硅宾与质子氢分子的氧化加成反应合成硅氢物种

doi:10.6023/cjoc202309007

有机化学 ›› 2024, Vol. 44 ›› Issue (4): 1311-1318.DOI: 10.6023/cjoc202309007 上一篇下一篇

研究论文

硅宾与质子氢分子的氧化加成反应合成硅氢物种

孔德亮, 杨萧昂, 赵怡玲, 彭彦博, 朱红平^*()

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

收稿日期:2023-09-07 修回日期:2023-10-24 发布日期:2023-11-23
作者简介:† 共同第一作者.
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

Deliang Kong, Xiaoang Yang, Yiling Zhao, Yanbo Peng, Hongping Zhu()

State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005

Received:2023-09-07 Revised:2023-10-24 Published:2023-11-23
Contact: * E-mail: hpzhu@xmu.edu.cn
About author:† The authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21972112); Productive Research Program of Fujian Province(2021H6002)

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摘要/Abstract

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(N^tBu)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.

关键词: 硅宾, 质子氢分子, 氧化加成反应, 硅氢化合物

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(N^tBu)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.

Key words: silylene, proton-containing molecule, oxidative addition reaction, hydrosilicon compound

引用此文

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.

Deliang Kong, Xiaoang Yang, Yiling Zhao, Yanbo Peng, Hongping Zhu. Synthesis of the Hydrosilicon Species via Oxidative Addition of Silylene toward the Proton-Containing Molecules[J]. Chinese Journal of Organic Chemistry, 2024, 44(4): 1311-1318.

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图/表 6

图式1. 化合物4~6的合成

Scheme 1. Synthesis of compounds 4~6

图式2. 化合物7~14的合成

Scheme 2. Synthesis of compounds 7~14

图式3. 化合物15的合成

Scheme 3. Synthesis of compound 15

图1. 化合物5的晶体分子结构图及重要的键长

Figure 1. X-ray crystal structure of 5 and the important bond lengths (nm) H atoms except for that of the SiH are omitted for clarity. Selected bond lengths (nm): Si(1)—O(1) 0.1647(2), Si(1)—N(2) 0.1731(2), Si(1)—N(3) 0.2734(2), Si(1)—N(4) 0.1753(2), Si(1)—H(1) 0.1460(20).

图2. 化合物7的晶体分子结构图及重要的键长

Figure 2. X-ray crystal structure of 7 and the important bond lengths (nm) H atoms except for that of the Si—H are omitted for clarity. Selected bond lengths (nm): Si(1)—S(1) 0.2182(7), Si(1)—N(1) 0.1786(2), Si(1)—N(2) 0.2127(2), Si(1)—N(3) 0.1818(2), Si(1)—H(1) 0.1417(17).

图3. 化合物11的晶体分子结构图及重要的键长

Figure 3. X-ray crystal structure of 11 and the important bond lengths (nm) H atoms except for that of the SiH are omitted for clarity. Selected bond lengths (nm): Si(1)—S(1) 0.2160(2), Si(1)—N(1) 0.1784(4), Si(1)—N(2) 0.1798(4), Si(1)—N(3) 0.2253(4), Si(1)—H(1) 0.1430(40).

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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

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