Synthesis and characterization of the first doubly-bridging pyridine-2-thionate (pys) molybdenum complex: crystal structure of [Mo(η3-C3H5)(CO)2]2(η1:η2:μ-pyS)2

The doubly-bridging pyridine-2-thionate (pyS) molybdenum complexes [Mo(η3-C3H4R)(CO)2]2(η1:η2:μ-pyS)2 (R=H, 1a; CH3, 1b) are accessible by the reaction of [Mo(η3-C3H4R)(CO)2(CH3CN)2Br] with pySK in CH2Cl2 at room temperature. Complexes 1a and 1b are dimers with each pyS unit chelating through sulfur and nitrogen to one metal center and bridging both metals through sulfur. Treatment of 1a with piperidine affords complex [Mo(η3-C3H5)(η2-pyS)(C5H10NH)(CO)2] (2). Complex 1a is characterized by X-ray diffraction analysis.