In:
Angewandte Chemie, Wiley, Vol. 129, No. 41 ( 2017-10-02), p. 12731-12734
Abstract:
The imidazolium chloride [C 3 H 3 N(C 3 H 6 NMe 2 )N{C(Me)(=NDipp)}]Cl ( 1 ; Dipp=2,6‐diisopropyl phenyl), a potential precursor to a tritopic N imine C NHC N amine pincer‐type ligand, reacted with [Ni(cod) 2 ] to give the Ni I ‐Ni I complex 2 , which contains a rare cod‐derived η 3 ‐allyl‐type bridging ligand. The implied intermediate formation of a nickel hydride through oxidative addition of the imidazolium C−H bond did not occur with the symmetrical imidazolium chloride [C 3 H 3 N 2 {C(Me)(=NDipp)} 2 ]Cl ( 3 ). Instead, a Ni−C(sp 3 ) bond was formed, leading to the neutral N imine CHN imine pincer‐type complex Ni[C 3 H 3 N 2 {C(Me)(=NDipp)} 2 ]Cl ( 4 ). Theoretical studies showed that this highly unusual feature in nickel NHC chemistry is due to steric constraints induced by the N substituents, which prevent Ni−H bond formation. Remarkably, ethylene inserted into the C(sp 3 )−H bond of 4 without nickel hydride formation, thus suggesting new pathways for the alkylation of non‐activated C−H bonds.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v129.41
DOI:
10.1002/ange.201706581
Language:
English
Publisher:
Wiley
Publication Date:
2017
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