Abstract
Addition of H2S(g) into DMF solution of complex [PPN][NiIII(OPh)(P(o-C6H3-3- SiMe3-2-S)3)] led to the formation of complex [PPN][NiIII(SH)(P(C6H3-3-SiMe3-2- S)3)] (1). Complex [PPN][NiIII(SSPh)(P(C6H3-3-SiMe3-2-S)3)] (2) was synthesized by reaction of complex 1 and diphenyl disulfide in 1:1 moalr ratio in DMF solution. Complexes 1 and 2, characterized by single-crystal X-ray diffraction, SQUID, EPR and UV-Vis, were mononulclear nickel(III) complexes and the geometry of the Ni center is a five-coordinate distorted trigonal bipyramidal. To the best of our knowledge, this work described the first direct synthesis of metal polysulfanido complexes. The reaction of complex 1 and HSCPh3 in 1:1 molar ratio in DMF yielded the [PPN]2[{Ni(P(o-C6H3-3-SiMe3-2-S)3)}2(μ-S6)] (3), characterized by single-crystal X-ray diffraction. Complex 3 is a dinuclear nickel(III) complex with S62- bridged ligand and the geometry of the Ni center is a five-coordinate distorted trigonal bipyramidal. To my best knowledge, complex 3 is the first dinuclear nickel complex linked by S62- chain.