Pyridine-2,6-dimethanethiolate and pyridine-2,6-dithiocarboxylate form sparingly soluble Ni-II pincer complexes formulated as [Ni(pdmt)](2) and [N(pdtc)](2), respectively, with two Ni-(mu(2)-S)-Ni bridges. In acetonitrile reaction systems, the latter undergoes die 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 Me3SiO-, RS- and L-0 Et3P 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. [N(pdtc)(OSiMe3)](1-)) deprotonates acetonitrile and acetone to form[N(pdtc)(CH2R)](1-) (R CN, COMe). Reaction of [N(pdtc)SEt](1-) with Fe-II yields the thiolate-bridged dimer {N(pdtc)](2)(SEt)(1-). Refluxing an acetonitrile solution of [N(pdtc)SH1- in air results information of trinuclear [N(pdtc)](3)S](2-) containing die rate unsupported Ni-3(mu(3)-S) bridge core. Reaction of [N(pdtc)CN1- with [Fe(Me(6)tren)(OTI)](1+) forms the complex [Ni(pdtc)CNFe(Me(6)tren)(1+), the only example of a single N-C 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 N-II thiolates, an extensive family of compounds, to produce mononuclear products.