Cleavage of Ni-(mu(2)-S)-Ni bridges in dinuclear nickel(II) dithiolate pincer complexes and related reactions.

ABSTRACT: Pyridine-2,6-dimethanethiolate and pyridine-2,6-dithiocarboxylate form sparingly soluble Ni(II) pincer complexes formulated as [Ni(pdmt)](2) and [Ni(pdtc)](2), respectively, with two Ni-(mu(2)-S)-Ni bridges. In acetonitrile reaction systems, the latter undergoes the facile bridge cleavage reactions [Ni(pdtc)](2) + 2L(0,-) --> 2[Ni(pdtc)L](0,-) with an extensive set of nucleophiles to afford planar mononuclear products with L(-) = halide, CN, Me(3)SiO(-), RS(-) and L(0) = Et(3)P and a N-heterocyclic carbene. [Ni(pdmt)](2) is considerably less reactive toward bridge disruption. Cleavage products support several reactions of interest leading to other mononuclear species and to di- and trinuclear complexes. [Ni(pdtc)(OSiMe(3))](1-) deprotonates acetonitrile and acetone to form [Ni(pdtc)(CH(2)R

SUBMITTER: Huang D 

PROVIDER: S-EPMC2878386 | biostudies-literature | 2009 Jul

REPOSITORIES: biostudies-literature