Synthesis and structural characterization of dimolybdenum(IV) and molybdenum(VI) complexes with trisbenzenethiolatophosphine ligands

The synthesis and crystal structures of two high valent molybdenum complexes containing trisbenzenethiolatophosphine ligands, [Mo2(PS3)2(PS3H)] (1) and [Mo(PS3″)2] (2), where PS3 = [P(C6H4-2-S)3]3−, PS3H = [P(C6H4-2-S)2(C6H4-2-SH)]2−, and PS3″ = [P(C6H3-3-Me3Si-2-S)3]3−, are described. Compound 1 is a dimeric Mo(IV) species containing three PS3 ligands with an uncoordinated thiol group. An intramolecular hydrogen bonding S–H⋯S was found in the structure. Two molybdenum ions are bridged by three thiolates. The geometry can be described as two pentagonal bipyramids sharing a triangle face formed by three bridging S atoms. Compound 2 is a Mo(VI) species binding with two tetradentate PS3″ ligands. The eight-coordinate molybdenum center adopts a dodecahedral geometry.