Syntheses, structures and catalytic properties of new mononuclear terpyridine-manganese(II) complexes with tetraphenylimido-diphosphinate and diphenylphosphinate ligands

摘要

Treatment of manganese(II) acetate tetrahydrate [Mn(CH3COO)(2)4H(2)O] with one equivalent of 2,2:6,2-terpyridine (terpy) and two equivalents of potassium tetraphenylimido-diphosphinate K[N(Ph2PO)(2)] in methanol afforded a mononuclear manganese(II) complex, [(terpy)Mn{(1)-O-N(Ph2PO)(2)}(2)(H2O)] (1), with two terminal [N(Ph2PO)(2)]- ligands. Interaction of [Mn(CH3COO)(2)4H(2)O] with one equivalent of terpy in the presence of both K[N(Ph2PO)(2)] and Ph2PO2K in methanol gave a mononuclear manganese(II) complex [(terpy)Mn((1)-O-O2PPh2){N(Ph2PO)(2)}] (2) with a chelated [N(Ph2PO)(2)]- ligand. Treatment of manganese(II) dichloride tetrahydrate [MnCl(2)4H(2)O] with three equivalents of K[N(Ph2PO)(2)] in methanol resulted in isolation of a mononuclear manganese(III) complex [Mn{(1)-O-N(Ph2PO)(2)}-{N(Ph2PO)(2)}(2)] (3) with one terminal and two chelated [N(Ph2PO)(2)]- ligands. Reaction of [Mn(CH3COO)(2)4H(2)O] with one equivalent of 4-phenyl-[2,2:6,2]-terpyridine (4-Ph-terpy) and two equivalents of Ph2PO2K in methanol gave [(4-Ph-terpy)Mn((1)-O-O2PPh2)(2)(H2O)] (4) with a labile water molecule. Complexes 1-4 have been spectroscopically characterized and their structures have been established by single-crystal X-ray diffraction. Catalytic behavior of 1 and 4 for sulfide oxidation was also investigated.