Coordination Properties of Non-Rigid Phosphinoyldithioformate Complexes of the [Mo2O2(µ-S)2]2+ Cation in Catalytic Sulfur Transfer Reactions with Thiiranes

Abstract

Two “Mo2O2S2”-based complexes with phosphinoyldithioformate ligands were synthesized from the metathesis reaction of [R2P(O)CS2]− with (Me4N)2[Mo2O2(µ-S)2(Cl)4] to give [Mo2O2(µ-S)2{R2P(O)CS2}2] (1; R = Ph, 2; R = Bn). The complexes were fully characterized, including the X-ray crystal structure for 1. Variable temperatures 31P NMR of 1 and 2 exhibit non-rigid behavior in solution where three and two coordination isomers were present, respectively. The organic substituent on the P atom greatly impacts the complex non-rigid properties and behavior. The catalytic activity of 1 and 2 towards sulfur atom transfer (SAT) using propylene sulfide and cyclohexene sulfide was explored, employing homogeneous reaction conditions at an ambient temperature on the NMR scale. The complexes showed distinctly different properties along with high conversions in short reaction times. A catalytic cycle consistent with the results is proposed.