Investigations of pyridine-2-thiol as a ligand:: Synthesis and X-ray structures of the mixed Mo-Mn dinuclear complex CpMoMn(CO)3(μ-CO)(μ-η2-pyS)(μ-η1-pyS), the electron-deficient trimolybdenum cluster CP3Mo3(μ-CO)2(μ-S)(μ3-S) (μ-η2-NC5H4), and the mononuclear CPMO(CO)2(μ-η2-pyS)

The reaction of Mn-2(CO)(6)(pyS)(2) (1) with (CpMo(CO)(3))(2) (2) at 110degreesC gives the heterodinuclear complex CpMoMn(CO)(3)(mu-CO)(mu-eta(2)-pyS))(mu-eta(1)-pyS) (3), the mononuclear molybdenum complex CpMo(CO)(2)(mu-eta(2)-pyS) (4), and the 46-electron trimolybdenum cluster Cp3Mo3(mu-CO)(2)(mu-S)(mu3-S)(mu-eta(2)-NC5H4) (5). Compound 4 could also be prepared in high yield from the reaction of 2 with pyridine-2-thiol at 110degreesC. Compound 3 represents a rare example of a Mo-Mn heterodinuclear complex containing a mu-eta(2)-pyridine-2-thiolato, a mu-eta(1)-pyridine-2-thiolato, and a cyclopentadienyl ligand. The 46-electron compound 5 represents a unique example of a trimolybdenum compound containing three cyclopentadienyl ligands, an ortho-metalated pyridyl ligand, a capping sulfido, a bridging sulfido, and two semibridging CO ligands. Curiously, although this complex is formally electron deficient, it is unreactive toward two-electron donors. The structures of all the compounds have been unambiguously established by single-crystal X-ray crystallography.