DARSTELLUNG UND EIGENSCHAFTEN VON UND REAKTIONEN MIT METALLHALTIGEN HETEROCYCLEN. XII. METALLORGANISCHE KOMPLEXE VON MANGAN UND RHENIUM MIT NUCLEOPHILEN ZENTREN AM METALL UND SCHWEFEL

Article abstract of DOI:10.1016/S0022-328X(00)82476-6

The binuclear anions Na2<(OC)4MPR2S>2 (M = Mn: R = CH3; M = Re: R = CH3, C6H5) are obtained by reduction of the thiophosphinous acid complexes (OC)4BrMPR2SH with sodium amalgam in dimethoxyethane.Only for M = Mn the metal-metal bond can be cleaved with excess sodium to give Na2<(CO)4MnP(CH3)2S>.With dimethyl sulfate and 1,3-dibromopropane both nucleophilic centers in Na2<(OC)4MnP(CH3)2S> react to give CH3Mn(CO)4P(CH3)2SCH3, and the six-membered, sulfur-containing metallacycle , respectively.The heterolytic cleavage of the Re-Re bond in Na2<(OC)4RePR2S>2 with (CH3O)2SO2 leads to the methylated complexes CH3Re(CO)4PR2SCH3.The newly prepared compounds are characterized by their IR, NMR, and mass spectra.