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Group 11 Borataalkene Complexes: Models for Alkene Activation
Author(s) -
Phillips Nicholas A.,
Kong Richard Y.,
White Andrew J. P.,
Crimmin Mark R.
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202100919
Subject(s) - chemistry , moiety , alkene , natural bond orbital , ligand (biochemistry) , transition metal , metal , group (periodic table) , stereochemistry , coordination complex , catalysis , oxidation state , crystallography , computational chemistry , density functional theory , organic chemistry , biochemistry , receptor
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. 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 π‐system. Through the preparation and analysis of a consistent series of group 11 complexes, we show that variation of the metal can impact the coordination mode and hence substrate activation.