Reinvestigation of the first structurally characterized metal-coordinated sulfenic acid complex

Single crystal X-ray diffraction studies reveal a new crystal morphology of [Ru(DPPBT)(DPPBT-O2)(DPPBT-OH)] (DPPBT = 2-(diphenylphosphine)benzenethiolate; DPPBT-O2 = 2-(diphenylphosphine)benzene-sulfinate; DPPBT-OH = 2-(diphenylphosphine)benzenesulfenic acid) in the monoclinic space group C2/c. The sulfenic acid hydrogen, which was only inferred in the previously reported P-1 structure, has been located and refined. Comparison of metric data from the C2/c structure with density functional theory optimized structures (B3LYP/LANL2DZ + 6–31g(d)) definitively confirms the assignment of the complex as the Ru(II) sulfenic acid.