Slippage between η2 and η1 coordination in Group 11 borataalkene complexes: models for alkene activation
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Published version
Author(s)
Phillips, Nicholas
Kong, Richard
White, Andrew
Crimmin, Mark Richard
Type
Journal Article
Abstract
A series of linear late transition metal (M = Cu, Ag, Au and Zn) complexes featuring a side-on [B=C] - containing ligand have been isolated and characterised. The [B=C] - moiety is isoelectronic with the C=C system of an alkene. Comparison across the series shows that in the solid-state, deviation between the η 2 and η 1 coordination mode occurs. The degree of slippage is greatest for Au > Ag > Cu. A related zinc complex containing two [B=C] - ligands was prepared as a further point of comparison for the η 1 coordination mode. The bonding in these new complexes has been interrogated by computational techniques (QTAIM, NBO, ETS-NOCV) and rationalised in terms of the Dewar-Chatt-Duncanson model. The combined structural and computational data provide unique insight into catalytically relevant linear d 10 complexes of Cu, Ag and Au. Slippage is proposed to play a key role in catalytic reactions of alkenes through disruption and polarisation of the p -system. Through the preparation and analysis of a consistent series of group 11 complexes, we show that variation of the metal can impact the degree of slippage and hence substrate activation.
Date Issued
2021-05-17
Date Acceptance
2021-02-17
Citation
Angewandte Chemie International Edition, 2021, 60 (21), pp.12013-12019
ISSN
1433-7851
Publisher
Wiley
Start Page
12013
End Page
12019
Journal / Book Title
Angewandte Chemie International Edition
Volume
60
Issue
21
Copyright Statement
© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
License URL
Sponsor
Commission of the European Communities
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/33605521
Grant Number
677367
Subjects
Boron
Coordination Chemistry
borataalkene
coinage metal
gold catalysis
Publication Status
Published
Coverage Spatial
Germany
Date Publish Online
2021-02-19