Heterometallic Cerium(IV) Perrhenate, Permanganate, and Molybdate Complexes Supported by the Imidodiphosphinate Ligand [N(i-Pr2PO)2]鈭?/sup>
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- 作者：Guo-Cang Wang ; Herman H. Y. Sung ; Feng-Rong Dai ; Wai-Hang Chiu ; Wai-Yeung Wong ; Ian D. Williams ; Wa-Hung Leung
- 刊名：Inorganic Chemistry
- 出版年：2013
- 出版时间：March 4, 2013
- 年：2013
- 卷：52
- 期：5
- 页码：2556-2563
- 全文大小：468K
- 年卷期：v.52,no.5(March 4, 2013)
- ISSN：1520-510X
文摘
Heterometallic cerium(IV) perrhenate, permanganate, and molybdate complexes containing the imidodiphosphinate ligand [N(i-Pr2PO)2]鈭?/sup> have been synthesized, and their reactivity was investigated. Treatment of Ce[N(i-Pr2PO)2]3Cl (1) with AgMO4 (M = Re, Mn) afforded Ce[N(i-Pr2PO)2]3(ReO4) (2) or Ce2[N(i-Pr2PO)2]6(MnO4)2 (3). In the solid state, 3 is composed of a [Ce2{N(i-Pr2PO)2}6(MnO4)]+ moiety featuring a weak Ce鈥揙Mn interaction [Ce鈥揙Mn distance = 2.528(8) 脜] and a noncoordinating MnO4鈥?/sup> counteranion. While 3 is stable in the solid state and acetonitrile solution, it decomposes readily in other organic solvents, such as CH2Cl2. 3 can oxidize ethylbenzene to acetophenone at room temperature. Treatment of 1 with AgBF4, followed by reaction with [n-Bu4N]2[MoO4], afforded [Ce{N(i-Pr2PO)2}3]2(渭-MoO4) (4). Reaction of trans-Ce[N(i-Pr2PO)2]2(NO3)2 (5), which was prepared from (NH4)2Ce(NO3)6 and K[N(i-Pr2PO)2], with 2 equiv of [n-Bu4N][Cp*MoO3] yielded trans-Ce[N(i-Pr2PO)2]2(Cp*MoO3)2 (6). 4 can catalyze the oxidation of methyl phenyl sulfide with tert-butyl hydroperoxide with high selectivity. The crystal structures of complexes 3鈥?b>6 have been determined.