A self-hydrosilylation of phosphanylhydrosilylalkynes promoted by B(C6F5)3? An experimental and mechanistic study

Yanting Huang; Xiaoping Wang; Yan Li; Ming-Chung Yang; Ming-Der Su; Hongping Zhu

doi:10.1039/C8CC09022J

A self-hydrosilylation of phosphanylhydrosilylalkynes promoted by B(C₆F₅)₃? An experimental and mechanistic study†

Yanting Huang,^a Xiaoping Wang,^a Yan Li,*^b Ming-Chung Yang,^c Ming-Der Su

*^cd and Hongping Zhu

*^a

Author affiliations

* Corresponding authors

^a State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China
E-mail: hpzhu@xmu.edu.cn

^b Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
E-mail: yli@hznu.edu.cn

^c Department of Applied Chemistry, National Chiayi University, Chiayi, Taiwan

^d Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung, Taiwan
E-mail: midesu@mail.ncyu.edu.tw

Abstract

Phosphanylhydrosilylalkynes Me₂HSiC [triple bond, length as m-dash] CPAr₂ (Ar = Ph, 1a; 4-MeC₆H₄, 1b) were synthesized, which reacted with B(C₆F₅)₃ to produce alkenes [(E)-(C₆F₅)₃BCH [double bond, length as m-dash] C(PAr₂)SiMe₂]₂ (2a and 2b) and (Z)-(C₆F₅)₂BCHC(PAr₂)SiMe₂(C₆F₅) (3a and 3b). The formation of 2a (or 2b) involved a Wrackmeyer's SiHMe₂ migration followed by Si–H addition across the C [triple bond, length as m-dash] C bond, whereas, that of 3a (or 3b) involved a similar mechanism with a further C₆F₅ migration. The B(C₆F₅)₃-promoted reaction of the Si-centered geminal H and CC groups is thus realized, which may be considered as a self-hydrosilylation. Mechanistic studies by both variable temperature NMR spectroscopy and DFT calculations were accomplished.

This article is part of the themed collection: Celebrating a Century of Excellency in Chemistry at Xiamen University

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Article information

DOI: https://doi.org/10.1039/C8CC09022J
Article type: Communication
Submitted: 13 Nov 2018
Accepted: 07 Jan 2019
First published: 07 Jan 2019

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Chem. Commun., 2019,55, 1494-1497

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A self-hydrosilylation of phosphanylhydrosilylalkynes promoted by B(C₆F₅)₃? An experimental and mechanistic study

Y. Huang, X. Wang, Y. Li, M. Yang, M. Su and H. Zhu, Chem. Commun., 2019, 55, 1494 DOI: 10.1039/C8CC09022J

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