Issue 10, 2014

Transmethylation of a four-coordinate nickel(i) monocarbonyl species with methyl iodide

Abstract

Three distinct oxidation states of a nickel carbonyl species, formally Ni(II), +1 and 0, (compounds 1, 2 and 3 respectively) have been realized using a (PNP)Ni scaffold (PNP = N[2-PiPr2-4-Me-C6H3]2). X-ray diffraction (XRD) studies of these carbonyl complexes show a geometrical change about the nickel center from square planar (1) to pyramidal (2) and pseudotetrahedral (3). Interestingly, the Ni–C bond distance of 2 is longer than that of 1 and 3 due to the electron population of the antibonding dx2y2 orbital. A difference in the reactivity of these nickel carbonyl species was clearly observed. Reaction of the monovalent nickel carbonyl species (2) with CH3I revealed the formation of (PNP)NiCOCH3 (4) via C–C bond coupling while the zerovalent congener (3) underwent an oxidative ligand substitution reaction.

Graphical abstract: Transmethylation of a four-coordinate nickel(i) monocarbonyl species with methyl iodide

Supplementary files

Article information

Article type
Edge Article
Submitted
14 Apr 2014
Accepted
23 May 2014
First published
23 May 2014

Chem. Sci., 2014,5, 3853-3858

Author version available

Transmethylation of a four-coordinate nickel(I) monocarbonyl species with methyl iodide

C. Yoo, S. Oh, J. Kim and Y. Lee, Chem. Sci., 2014, 5, 3853 DOI: 10.1039/C4SC01089B

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