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A d 10 Ni–(H 2 ) Adduct as an Intermediate in HH Oxidative Addition across a NiB Bond
Author(s) -
Harman W. Hill,
Lin TzuPin,
Peters Jonas C.
Publication year - 2014
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.201308175
Subject(s) - adduct , borane , chemistry , ligand (biochemistry) , bifunctional , nickel , crystallography , oxidative addition , transition metal , metal , bond cleavage , catalysis , stereochemistry , nuclear magnetic resonance spectroscopy , organic chemistry , biochemistry , receptor
Bifunctional EH activation offers a promising approach for the design of two‐electron‐reduction catalysts with late first‐row metals, such as Ni. To this end, we have been pursuing H 2 activation reactions at late‐metal boratranes and herein describe a diphosphine–borane‐supported Ni—(H 2 ) complex, [( Ph DPB i Pr )Ni(H 2 )], which has been characterized in solution. 1 H NMR spectroscopy confirms the presence of an intact H 2 ligand. A range of data, including electronic‐structure calculations, suggests a d 10 configuration for [( Ph DPB i Pr )Ni(H 2 )] as most appropriate. Such a configuration is highly unusual among transition‐metal H 2 adducts. The nonclassical H 2 adduct is an intermediate in the complete activation of H 2 across the NiB interaction. Reaction‐coordinate analysis suggests synergistic activation of the H 2 ligand by both the Ni and B centers of the nickel boratrane subunit, thus highlighting an important role of the borane ligand both in stabilizing the d 10 Ni—(H 2 ) interaction and in the H—H cleavage step.