Tetravalent Titanium, Zirconium, and Cerium Oxo and Peroxo Complexes Containing an Imidodiphosphinate Ligand
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- 作者：Guo-Cang Wang ; Herman H. Y. Sung ; Ian D. Williams ; Wa-Hung Leung
- 刊名：Inorganic Chemistry
- 出版年：2012
- 出版时间：March 19, 2012
- 年：2012
- 卷：51
- 期：6
- 页码：3640-3647
- 全文大小：396K
- 年卷期：v.51,no.6(March 19, 2012)
- ISSN：1520-510X
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.