Tetravalent Titanium, Zirconium, and Cerium Oxo and Peroxo Complexes Containing an Imidodiphosphinate Ligand
文摘
Dinuclear Ti(IV), Zr(IV), and Ce(IV) oxo and peroxo complexes containing the imidodiphosphinate ligand [N(i-Pr2PO)2]鈭?/sup> have been synthesized and structurally characterized. Treatment of Ti(O-i-Pr)2Cl2 with KN(i-Pr2PO)2 afforded the Ti(IV) di-渭-oxo complex [Ti{N(i-Pr2PO)2}2]2(渭-O)2 (1) that reacted with 35% H2O2 to give the peroxo complex Ti[N(i-Pr2PO)2]2(畏2-O2) (2). Treatment of HN(i-Pr2PO)2 with Zr(O-t-Bu)4 and Ce2(O-i-Pr)8(i-PrOH)2 afforded the di-渭-peroxo-bridged dimers [M{N(i-Pr2PO)2}2]2(渭-O2)2 [M = Zr (3), Ce (4)]. 4 was also obtained from the reaction of Ce[N(i-Pr2PO)2]3 with 35% H2O2. Treatment of (Et4N)2[CeCl6] with 3 equiv of KN(i-Pr2PO)2 afforded Ce[N(i-Pr2PO)2]3Cl (5). Reaction of (Et4N)2[CeCl6] with 2 equiv of KN(i-Pr2PO)2 in acetonitrile, followed by treatment with Ag2O, afforded the 渭-oxo-bridged complex [Ce{N(i-Pr2PO)2}Cl]2[渭-N(i-Pr2PO)2]2(渭-O) (6). 6 undergoes ligand redistribution in CH2Cl2 in air to give 5. The solid-state structures of [K2{N(i-Pr2PO)2}2(H2O)8]n and complexes 1鈥?b>6 have been determined.