Molybdenum compounds bearing pymS (pyrimidine-2-thiolato) and tertiary phosphine ligands

741-746In this paper we have reported mono- and dinuclear molybdenum compounds containing doubly bridging pymS (pyrimidine-2-thiolato) and P(Fu)3 {(Fu = (2-furyl)phosphine)} or P(OMe)3 (trimethyl phosphite). One-pot reaction between [Mo(CO)3(NCMe)3] and pymSH (pyrimidine-2-thiol) in the presence of P(Fu)3 in THF at 50 °C gives the previously reported eight coordinate compound [Mo(к2-pymS)4] (1) in 17% yield and two new compounds [Mo(CO)4(P(Fu)3)2] (2) and [Mo2(CO)4(μ-к2-pymS)2(P(Fu)3)2] (3) in 51 and 15% yields, respectively. A similar reaction involving P(OMe)3 furnishes two mononuclear compounds [Mo(CO)2(κ2-pyS)2(P(OMe)3)] (4) and [Mo(CO)4(P(OMe)3)2] (5) in 20 and 35% yields, respectively. Compounds 2 and 4 are characterized by single-crystal X-ray diffraction analysis in addition to IR, 1H NMR and 31P{1H} NMR spectroscopic methods