REACTIONS OF METAL-DISULFUR COMPLEXES WITH NUCLEOPHILES AND ELECTROPHILES

New synthetic methods for the preparation of the disulfur complexes of molybdenum MoOS2(S2CNR2)2 (where [formula ommited] are described. The reactions of these disulfur complexes with a series of nucleophiles, [formula ommited] have been characterized, and in each case the sulfur-substituted nucleophile (S-N) and MoO(S2CNR2)2 are produced. Reaction of MoOS2(S2CNR2)2 with C6H5SH or C6H5S- yields the dimeric molybdenum(V) complex Mo2O2S2(S2CNR2)2. The molybdenum-disulfur complexes do not react with the electrophile CH3I, but reaction with CH3SO3F produces a new complex containing a persulfide ligand, [MoO(SSCH3)(S2CNR2)2]+. Characteristics of the synthetic molybdenum complexes are compared to those of certain molybdoenzymes which have been found to contain labile sulfur atoms. Reactions of the coordinated disulfur ligand in IrS2(dppe)2Cl (where dppe = bis(diphenylphosphino)ethane) have also been studied. In contrast to the molybdenum systems, no reactions occur with the common thiophiles P(C6H5)3, P(OC2H5)3, and CN-. Methyl fluorosulfonate reacts to form a persulfide complex of Ir(III), [Ir(SSCH3)(dppe)2],2+ which has been characterized by 1H and 31P NMR, conductivity studies, and analytical data. © 1979, American Chemical Society. All rights reserved.