Molybdenum and rhenium carbonyl complexes containing thiolato ligands

Abstract

The reaction of fac-[M(OTf)(CO)3(N–N)](M = Mn, Re; N–N = 2,2′-bipyridine, 1,10-phenanthroline) complexes with in situ generated LiSEt afforded immediately, in THF at low temperature, the corresponding mononuclear terminal thiolato complexes fac-[M(SEt)(CO)3(N–N)](1-2a,b). Using an analogous synthetic strategy, tungsten and molybdenum (II) alkyl- and arylthiolatos of formula cis-[M(SR)(η3-allyl)(CO)2(N–N)] (3-6a,b) have been obtained. Preliminary reactions of the more reactive molybdenum thiolato complexes towards dimethylacetylenedicarboxylate led to Z-alkenyl products (7a,b), resulting from the insertion of the organic unsaturated electrophile into the Mo–S bond. For each new type of compound, one representative has been characterized in the solid state by X-ray diffraction.