Synthesis, structure and bonding of new mono- and dinuclear molybdenum complexes containing pyridine-2-thiolate (pyS) and different P-donors.

Three new molybdenum complexes have been synthesized from one-pot reactions between Mo(CO) 3 (NCMe) 3 and pyridine-2-thiol (pySH) in the presence of different P-donors. Reaction with P(OMe) 3 in MeCN at ca. 55 °C gives Mo(CO) 2 [P(OMe) 3 ](κ 2 -pyS) 2 ( 1 ) and Mo(CO) 4 [P(OMe) 3 ] 2 ( 2 ). A similar reaction involving bis(diphenylphosphino)methane (dppm) furnishes the dinuclear species Mo 2 (CO) 4 (μ,κ 2 -pyS) 2 (κ 2 -dppm) ( 3 ) together with the mononuclear complexes Mo(CO)(κ 2 -pyS) 2 (κ 2 -dppm) ( 4 ) and Mo(CO) 4 (κ 2 -dppm) ( 5 ). With bis(diphenylphosphino)ethane (dppe) only the mononuclear complexes Mo(CO)(κ 2 -pyS) 2 (κ 2 -dppe) ( 6 ), Mo(CO) 4 (κ 2 -dppe) ( 7 ), and Mo(CO) 3 (κ 1 -dppe)(κ 2 -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. [ABSTRACT FROM AUTHOR]