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- Title
Tritopic NHC Precursors: Unusual Nickel Reactivity and Ethylene Insertion into a C(sp<sup>3</sup>)-H Bond.
- Authors
Ren, Xiaoyu; Gourlaouen, Christophe; Wesolek, Marcel; Braunstein, Pierre
- Abstract
The imidazolium chloride [C3H3N(C3H6NMe2)N{C(Me)(=NDipp)}]Cl ( 1; Dipp=2,6-diisopropyl phenyl), a potential precursor to a tritopic NimineCNHCNamine pincer-type ligand, reacted with [Ni(cod)2] to give the NiI-NiI complex 2, which contains a rare cod-derived η3-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 [C3H3N2{C(Me)(=NDipp)}2]Cl ( 3). Instead, a Ni−C(sp3) bond was formed, leading to the neutral NimineCHNimine pincer-type complex Ni[C3H3N2{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(sp3)−H bond of 4 without nickel hydride formation, thus suggesting new pathways for the alkylation of non-activated C−H bonds.
- Subjects
NICKEL; ETHYLENE; CHEMICAL precursors; REACTIVITY (Chemistry); CARBON-hydrogen bonds
- Publication
Angewandte Chemie, 2017, Vol 129, Issue 41, p12731
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201706581