B(C6F5)(3): catalyst or initiator? insights from computational studies into surrogate silicon chemistry

TitleB(C6F5)(3): catalyst or initiator? insights from computational studies into surrogate silicon chemistry
Publication TypeJournal Article
Year of Publication2018
AuthorsBanerjee, S, Vanka, K
JournalACS Catalysis
Volume8
Issue7
Pagination6163-6176
Date PublishedJUL
Type of ArticleArticle
ISSN2155-5435
Keywordsautocatalysis, Density functional theory, ion-pair, Lewis acid catalysis, reaction mechanism, surrogate silicone chemistry, tris(pentafluorophenyl)borane
Abstract

One of the most promising recent developments in catalysis has been the use of the metal-free Lewis acid B(C6F5)(3) as a catalyst for a range of different chemical transformations. Perhaps the most impressive achievement in this regard is the recently accomplished in situ generation of SiH4 from surrogates (Simonneau and Oestreich, Nat. Chem., 2015,7, 816). However, what the current computational work, with density functional theory, reveals is that this process, in addition to being catalyzed by B(C6F5)(3), is also significantly dominated by a series of autocatalytic reactions. The results are further corroborated by the use of the energetic span model, which shows that the turnover frequency is higher for the newly proposed autocatalytic pathway in comparison to the conventional B(C6F5)(3)-catalyzed pathway. The current work therefore provides interesting new insights into surrogate silicon chemistry. But, more importantly, the current studies indicate that B(C6F5)(3) is likely to function more as an initiator rather than a pure catalyst in many metal-free transformations that have been reported to date.

DOI10.1021/acscatal.7b04489
Type of Journal (Indian or Foreign)

Foreign

Impact Factor (IF)

10.614

Divison category: 
Physical and Materials Chemistry