Exploring structural and electronic effects in three isomers of tris{bis(trifluoromethyl)phenyl}borane: Towards the combined electrochemical-frustrated Lewis pair activation of H2

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.

Item Type: Article
Additional Information: This article is licensed under a Creative Commons Attribution 3.0 Unported Licence
Faculty \ School: Faculty of Science > School of Chemistry
UEA Research Groups: Faculty of Science > Research Groups > Biophysical Chemistry (former - to 2017)
Faculty of Science > Research Groups > Physical and Analytical Chemistry (former - to 2017)
Faculty of Science > Research Groups > Synthetic Chemistry (former - to 2017)
Faculty of Science > Research Groups > Chemistry of Light and Energy
Faculty of Science > Research Groups > Chemistry of Life Processes
Faculty of Science > Research Centres > Centre for Molecular and Structural Biochemistry
Faculty of Science > Research Groups > Centre for Photonics and Quantum Science
Depositing User: Pure Connector
Date Deposited: 03 Aug 2015 09:22
Last Modified: 09 Feb 2023 13:40
URI: https://ueaeprints.uea.ac.uk/id/eprint/53996
DOI: 10.1039/c5dt01918d

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