496862-82-9Relevant academic research and scientific papers
An electrochemical study of frustrated lewis pairs: A metal-free route to hydrogen oxidation
Lawrence, Elliot J.,Oganesyan, Vasily S.,Hughes, David L.,Ashley, Andrew E.,Wildgoose, Gregory G.
supporting information, p. 6031 - 6036 (2014/05/20)
Frustrated Lewis pairs have found many applications in the heterolytic activation of H2 and subsequent hydrogenation of small molecules through delivery of the resulting proton and hydride equivalents. Herein, we describe how H2 can be preactivated using classical frustrated Lewis pair chemistry and combined with in situ nonaqueous electrochemical oxidation of the resulting borohydride. Our approach allows hydrogen to be cleanly converted into two protons and two electrons in situ, and reduces the potential (the required energetic driving force) for nonaqueous H2 oxidation by 610 mV (117.7 kJ mol-1). This significant energy reduction opens routes to the development of nonaqueous hydrogen energy technology.
B(C6F5)3 catalyzed hydrosilation of enones and silyl enol ethers
Blackwell, James M,Morrison, Darryl J,Piers, Warren E
, p. 8247 - 8254 (2007/10/03)
The 1,4 hydrosilation of a variety of simple α,β-unsaturated enones as catalyzed by B(C6F5)3 (1-2%) is described. For substrates with no steric hindrance near the β-carbon, 1,4 addition of silane is very clean; in other instances, 1,2 hydrosilation is competitive. The reaction is facile with five commercially available silane reagents. For two examples, a novel hydrosilation of the resulting silylenol ethers was also observed. The net trans stereochemistry of H-Si addition to the silylenol ether C=C bond was established and points to a stepwise mechanism for this reaction. This was supported by the observation and full spectroscopic characterization of a silylcarboxonium ion intermediate with an [HB(C6F5)3]- counteranion in the hydrosilation of the silylenol ether derived from 4,4-dimethyl-2-cyclohexen-1-one and PhMe2SiH.
