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., 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
    Depositing User: Pure Connector
    Date Deposited: 03 Aug 2015 10:22
    Last Modified: 11 Jun 2019 11:32
    URI: https://ueaeprints.uea.ac.uk/id/eprint/53996
    DOI: 10.1039/c5dt01918d

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