01982nas a2200241   4500008004100000022001400041245010800055210006900163260000800232300001400240490000600254520113500260653001801395653003001413653001301443653002501456653002301481653003301504653003401537100002501571700001701596856012701613       2018                        eng d  a2155-543500aB(C6F5)(3): catalyst or initiator? insights from computational studies into surrogate silicon chemistry0 aBC6F53 catalyst or initiator insights from computational studies  cJUL  a6163-61760 v83 a<p>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.</p>10aautocatalysis10aDensity functional theory10aion-pair10aLewis acid catalysis10areaction mechanism10asurrogate silicone chemistry10atris(pentafluorophenyl)borane1 aBanerjee, Subhrashis1 aVanka, Kumar  uhttps://library.ncl.res.in/content/bc6f53-catalyst-or-initiator-insights-computational-studies-surrogate-silicon-chemistry