Useful Method for the Preparation of Low-Coordinate Nickel(I) Complexes via Transformations of the Ni(I) Bis(amido) Complex K{Ni[N(SiMe3)(2,6- i Pr2-C6H3)]2}

ABSTRACT: A convenient method of preparing two- and three-coordinate Ni(I) complexes of the form L-NiI-X (L = P t Bu3, P i Pr3, DPPE, NHC; X = -N(SiMe3)(2,6- i Pr-C6H3), -O(2,6- t Bu2-4-Me-C6H2)) is reported. Protonation of the easily prepared anionic Ni(I) bis(amido) complex K{Ni[N(SiMe3)(2,6- i Pr-C6H3)]2} in the presence of an appropriate L-type ligand results in loss of HN(SiMe3)(2,6- i Pr-C6H3) and trapping of the resulting neutral Ni(I)-amido fragment to yield neutral, paramagnetic, two- and three-coordinate Ni(I) complexes. Protonation of these neutral amido complexes by the bulky phenol HO(2,6- t Bu2-4-Me-C6H2) results in loss of the second amido moiety and trapping by the resulting phenoxide to yield Ni(I)-O(2,6- t Bu2-4-Me-C6H2) complexes. The hapticity of the phenoxide ligand is influenced by the ?-accepting ability of the L-type ligand. Where L = P t Bu3, a poor ?-acceptor, the phenoxide acts as a ?-acceptor and adopts a ?5-bonding mode through dearomatization of the phenyl ring. When L = NHC, a competent ?-acceptor, the phenoxide acts as a ?-donor, adopting a ?1-bonding mode through the O atom. The modular nature of this synthetic strategy allows variation of both the L- and X-type ligands of the complex in a stepwise fashion and should be extendable to a wide variety of ligand types for new Ni(I) complexes.

SUBMITTER: Lipschutz MI 

PROVIDER: S-EPMC4195509 | biostudies-literature | 2014 Oct

REPOSITORIES: biostudies-literature