A new mode of chemical reactivity for metal-free hydrogen activation by Lewis acidic boranes
File(s)
Author(s)
Type
Journal Article
Abstract
We herein explore whether tris(aryl)borane Lewis acids are capable of cleaving H2 outside of the usual Lewis acid/base chemistry described by the concept of frustrated Lewis pairs (FLPs). Instead of a Lewis base we use a chemical reductant to generate stable radical anions of two highly hindered boranes: tris(3,5-dinitromesityl)borane and tris(mesityl)borane. NMR spectroscopic characterization reveals that the corresponding borane radical anions activate (cleave) dihydrogen, whilst EPR spectroscopic characterization, supported by computational analysis, reveals the intermediates along the hydrogen activation pathway. This radical-based, redox pathway involves the homolytic cleavage of H2 , in contrast to conventional models of FLP chemistry, which invoke a heterolytic cleavage pathway. This represents a new mode of chemical reactivity for hydrogen activation by borane Lewis acids.
Date Issued
2019-06-17
Date Acceptance
2019-04-09
Citation
Angewandte Chemie - International Edition, 2019, 58 (25), pp.8362-8366
ISSN
0570-0833
Publisher
Wiley
Start Page
8362
End Page
8366
Journal / Book Title
Angewandte Chemie - International Edition
Volume
58
Issue
25
Copyright Statement
© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution‐NonCommercial‐NoDerivs License (http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
Sponsor
The Royal Society
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
The Royal Society
The Royal Society
The Royal Society
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/30968535
Grant Number
UF110061
EP/N026004/1
n/a
UF160395
RGF\EA\180179
RG2010/R2
Subjects
Lewis acids
boranes
dihydrogen
electron paramagnetic resonance
radicals
Publication Status
Published
Coverage Spatial
Germany
Date Publish Online
2019-04-09