Synthesis and structural characterization of trithiocarbonate complexes of molybdenum and ruthenium derived from CS<inf>2</inf> ligand

In an effort to synthesize trithiocarbonate complexes of molybdenum and ruthenium, we carried out the reaction of CS2 with the intermediates, obtained from the reaction of [Cp#ML3X], (1: Cp# = C5Me5, M = Mo, L1 = L2 = L3 = CO, X = Me; 2: Cp# = C5H5, M = Ru, L1 = L2 = PPh3, X = Cl and 3: Cp# = C5H5, M = Fe, L1 = L2 = CO, X = I) and [LiBH4⋅thf]. The reactions led to formation of the trithiocarbonate complexes [Cp*Mo(CO)2(μ-ɳ2:ɳ1-CS3)(CO)3MoCp*] (4) [Cp*Mo(CO)2(ɳ2-S2CSMe)] (5) and [Cp*Mo(CO)2(ɳ2-S2CMe)] (6) in moderate yields. Treatment of [CpRu(PPh3)2Cl] (2) with [LiBH4⋅thf] followed by mild pyrolysis of CS2 yielded the trithiocarbonate ruthenium complex [CpRuPPh3(ɳ2-S2CSMe)] (7). All the new compounds have been characterized by various spectroscopic techniques and the structures of compounds 4, 5 and 7 were unequivocally established by crystallographic analysis.