posted on 2015-09-14, 00:00authored byChangho Yoo, Manjaly
J. Ajitha, Yousung Jung, Yunho Lee
An open-shell reaction of the nickel(I)
carbonyl species (PNP)Ni-CO
(1) with iodoalkanes has been explored experimentally
and theoretically. The initial iodine radical abstraction by a nickel(I)
carbonyl species was suggested to produce (PNP)Ni-I (4) and the concomitant alkyl radical, according to a series of experimental
indications involving stoichiometric controls employing iodoalkanes.
Corresponding alkyl radical generation was also confirmed by radical
trapping experiments using Gomberg’s dimer. Molecular modeling
supports that the nickel acyl species (PNP)Ni-COCH3 (2) can be formed by a direct C–C bond formation between
a carbonyl ligand of 1 and a methyl radical. As an alternative
pathway, the five-coordinate intermediate species (PNP)Ni(CO)(CH3) (5) that involves both CO and CH3 binding at a nickel(II) center is also suggested with a comparable
activation barrier, although this pathway energetically favors the
formation of (PNP)Ni-CH3 (3) via a barrierless
elimination of CO over a CO migratory insertion. Thus, our present
work supports that the direct C–C bond coupling occurs between
an alkyl radical and the carbonyl ligand at a monovalent nickel center
in the generation of an acyl product.