Synthesis and dimer cleavage reactions of the N2S thiolate bridged dimer [(mmp-dach)2Ni2]Cl2
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The facile synthesis of a monoderivatized N2S ligand based on the cyclic diamine diazacycloheptane provides a tridentate donor which coordinates nickel(II), yielding a dithiolate bridged nickel dimer with a hinge angle of 135.7° and acute N-Ni-N bite angles of ca. 80°. Dimer splitting occurs on reaction with iodoacetamide, producing an S-alkylated octahedral complex. Cyanide also cleaves the dimer, resulting in a cyanide-bound N2S square planar monomer with two nucleophilic sites, thiolate-S and cyanide-N. Molecular structures of the dimeric cation, [(mmp-dach)2Ni2]Cl2, the iodoacetamide derivative, [(dtp-dach)Ni(MeCN)2]Cl2, and an S-oxygenate, [(smp-dach)-Ni(CN)], are reported. © 1999 American Chemical Society.
author list (cited authors)
Grapperhaus, C. A., Bellefeuille, J. A., Reibenspies, J. H., & Darensbourg, M. Y.