Si-B Functional Group Exchange Reaction Enabled by a Catalytic Amount of BH3: Scope, Mechanism, and Application

Zhang, Jiong1,2; Wei, Rui3,4; Ren, Chunping1; Liu, Liu Leo3,4; Wu, Lipeng1

2023-07-01

10.1021/jacs.3c05625

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   影响因子和分区

0002-7863

1520-5126

Functional group exchanges based on single-bond transformationare rare and challenging. In this regard, functional group exchangereactions of hydrosilanes proved to be more problematic. This is becausethis exchange requires the cleavage of the C-Si bond, whilethe Si-H bond is relatively easily activated for hydrosilanes.Herein, we report the first Si-B functional group exchangereactions of hydrosilanes with hydroboranes simply enabled by BH3 as a catalyst. Our methodology works for various aryl andalkyl hydrosilanes and different hydroboranes with the tolerance ofgeneral functional groups (up to 115 examples). Control experimentsand density functional theory (DFT) studies reveal a distinct reactionpathway that involves consecutive C-Si/B-H and C-B/B-H & sigma;-bond metathesis. Further investigations of using more readilyavailable chlorosilanes, siloxane, fluorosilane, and silylborane forSi-B functional group exchanges, Ge-B functional groupexchanges, and depolymerizative Si-B exchanges of polysilanesare also demonstrated. Moreover, the regeneration of MeSiH3 from polymethylhydrosiloxane (PMHS) is achieved. Notably, the formalhydrosilylation of a wide range of alkenes with SiH4 andMeSiH(3) to selectively produce (chiral)trihydrosilanes and(methyl)dihydrosilanes is realized using inexpensive and readily availablePhSiH(3) and PhSiH2Me as gaseous SiH4 and MeSiH3 surrogates.

SCI ; EI ; IC ; CCR

英语

NI论文

通讯

National Natural Science Foundation of China["22271295","22271132"] ; Major Program of the Lanzhou Institute of Chemical Physics, CAS[ZYFZFX-9] ; State Key Laboratory Program of the Lanzhou Institute of Chemical Physics[CHGZ-202208] ; Guangdong Innovation amp; Entrepreneurial Research Team Program[2021ZT09C278]

Chemistry

Chemistry, Multidisciplinary

WOS:001023564600001

AMER CHEMICAL SOC

20232914399195

Chemical bonds ; Chemical reactions ; Density functional theory ; Germanium compounds ; Polysilanes ; Silicon

Nonferrous Metals and Alloys excluding Alkali and Alkaline Earth Metals:549.3 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Inorganic Polymers:815.1.2 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

Web of Science

1.Chinese Acad Sci, Lanzhou Inst Chem Phys LICP, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China
2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
4.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China

Zhang, Jiong,Wei, Rui,Ren, Chunping,et al. Si-B Functional Group Exchange Reaction Enabled by a Catalytic Amount of BH3: Scope, Mechanism, and Application[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2023,145(28):15619-15629.

Zhang, Jiong,Wei, Rui,Ren, Chunping,Liu, Liu Leo,&Wu, Lipeng.(2023).Si-B Functional Group Exchange Reaction Enabled by a Catalytic Amount of BH3: Scope, Mechanism, and Application.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,145(28),15619-15629.

Zhang, Jiong,et al."Si-B Functional Group Exchange Reaction Enabled by a Catalytic Amount of BH3: Scope, Mechanism, and Application".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 145.28(2023):15619-15629.