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Haque, Mohd Rezaul
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article
Synthesis, structure and bonding of new mono- and dinuclear molybdenum complexes containing pyridine-2-thiolate (pyS) and different P-donors
Abstract
<p>Three new molybdenum complexes have been synthesized from one-pot reactions between Mo(CO)<sub>3</sub>(NCMe)<sub>3</sub> and pyridine-2-thiol (pySH) in the presence of different P-donors. Reaction with P(OMe)<sub>3</sub> in MeCN at ca. 55 °C gives Mo(CO)<sub>2</sub>[P(OMe)<sub>3</sub>](κ<sup>2</sup>-pyS)<sub>2</sub> (1) and Mo(CO)<sub>4</sub>[P(OMe)<sub>3</sub>]<sub>2</sub> (2). A similar reaction involving bis(diphenylphosphino)methane (dppm) furnishes the dinuclear species Mo<sub>2</sub>(CO)<sub>4</sub>(μ,κ<sup>2</sup>-pyS)<sub>2</sub>(κ<sup>2</sup>-dppm) (3) together with the mononuclear complexes Mo(CO)(κ<sup>2</sup>-pyS)<sub>2</sub>(κ<sup>2</sup>-dppm) (4) and Mo(CO)<sub>4</sub>(κ<sup>2</sup>-dppm) (5). With bis(diphenylphosphino)ethane (dppe) only the mononuclear complexes Mo(CO)(κ<sup>2</sup>-pyS)<sub>2</sub>(κ<sup>2</sup>-dppe) (6), Mo(CO)<sub>4</sub>(κ<sup>2</sup>-dppe) (7), and Mo(CO)<sub>3</sub>(κ<sup>1</sup>-dppe)(κ<sup>2</sup>-dppe) (8) resulted. Complexes 1, 3, and 6 have been characterized by single-crystal X-ray diffraction analyses and the bonding in 1 and 3 has been evaluated by density functional theory (DFT) calculations, optimized structures being discussed relative to the observed solid-state structures.</p>