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

Supplementary files

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

Download Citation

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

Permissions

Request permissions

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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Chemical Communications