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

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)](1-) (R = CN, COMe). Reaction of [Ni(pdtc)SEt](1-) with Fe(II) yields the thiolate-bridged dimer {[Ni(pdtc)](2)(SEt)}(1-). Refluxing an acetonitrile solution of [Ni(pdtc)SH](1-) in air results in formation of trinuclear [Ni(pdtc)](3)S](2-) containing the rare unsupported Ni(3)(mu(3)-S) bridge core. Reaction of [Ni(pdtc)CN](1-) with [Fe(Me(6)tren)(OTf)](1+) forms the complex [Ni(pdtc)CNFe(Me(6)tren)](1+), the only example of a single Ni-C[triple bond]N-Fe bridge within a molecule. Structures of the various types of reaction products are presented. This work demonstrates the potential utility of bridge cleavage of polynuclear Ni(II) thiolates, an extensive family of compounds, to produce mononuclear products.