Transmethylation of a four-coordinate nickel (I) monocarbonyl species with methyl iodide
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 dx2− y2 orbital. A difference in the …
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 dx2− y2 orbital. A difference in the …
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 dx2−y2 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.
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