Reactions of [(η-C5H5)(CO)FeC(S)SC(Fp)S] (Fp = (η-C5H5)Fe(CO)2) with Group IB and IIB metals; X-ray molecular structure of [(η-C5H5)(CO)FeC(SHgBr2)SC(Fp)S]2

The reactions of the metallacyclic complex [Cp(CO)FeC(S)SC(Fp)S] (1) (Cp = η-C5H5) with Group IB and IIB metal compounds have been investigated. Electrophilic addition at the thione sulphur atom has been observed in all cases. The reactions of 1 with the coinage metal complexes [MX(PPh3)]n (M = Cu, X = I, n = 4; M = Ag, X = Cl, n = 4; M = Au, X = Cl, n = 1) in the presence of TlPF6 give the adducts [Cp(CO)FeC{SM(PPh3)}SC(Fp)S]PF6 (2), which have been characterizded spectroscopically. The mercury salt [HgMe]PF6 reacts similarly with 1 to afford [Cp(CO)FeC(SHgMe)SC(Fp)S]PF6 (3), whereas mercury dihalides give products that have been shown by an X-ray diffraction study in the case in which X = Br to be halogen-bridged dimers of the type [Cp(CO)FeC(SHgX2)SC(Fp)S]2. The bromine-bridged dimer displays Ci symmetry. The coordination around the Hg atoms involves four normal and one weak bonds, and the geometry can be described as a distorted trigonal bipyramid. Zinc chloride reacts with 1 to give an air-sensitive unstable derivative that is tentatively formulated as [Cp(CO)FeC(SZnCl2)SC(Fp)S]. © 1990.