Blagg, Robin J., Lawrence, Elliot J., Resner, Katie, Oganesyan, Vasily S.
ORCID: https://orcid.org/0000-0002-8738-1146, Herrington, Thomas J., Ashley, Andrew E. and Wildgoose, Gregory G.
(2016)
Exploring structural and electronic effects in three isomers of tris{bis(trifluoromethyl)phenyl}borane: Towards the combined electrochemical-frustrated Lewis pair activation of H2.
Dalton Transactions, 45 (14).
pp. 6023-6031.
ISSN 1477-9226
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Abstract
Three structural isomers of tris{bis(trifluoromethyl)phenyl}borane have been studied as the acidic com- ponent of frustrated Lewis pairs. While the 3,5-substituted isomer is already known to heterolytically cleave H2 to generate a bridging-hydride; ortho-substituents in the 2,4- and 2,5-isomers quench such reactivity through electron donation into the vacant boron pz orbital and steric blocking of the boron centre; as shown by electrochemical, structural and computational studies. Electrochemical studies of the corresponding borohydrides identify that the two-electron oxidation of terminal-hydrides occurs at more positive potentials than observed for [HB(C6F5)3]−, while the bridging-hydride oxidizes at a higher poten- tial still, comparable to that of free H2.
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