Heterometallic cerium(IV) perrhenate, permanganate, and molybdate complexes supported by the imidodiphosphinate ligand [N(i -Pr2PO) 2]-

Guo Cang Wang, Herman H.Y. Sung, Feng Rong Dai, Wai Hang Chiu, Wai Yeung WONG, Ian D. Williams, Wa Hung Leung*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

8 Citations (Scopus)

Abstract

Heterometallic cerium(IV) perrhenate, permanganate, and molybdate complexes containing the imidodiphosphinate ligand [N(i-Pr2PO) 2]- 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-Pr 2PO)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-OMn interaction [Ce-OMn distance = 2.528(8) Å] and a noncoordinating MnO4- 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-Pr 2PO)2}3]2(μ-MoO4) (4). Reaction of trans-Ce[N(i-Pr2PO)2]2(NO 3)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 3-6 have been determined.

Original languageEnglish
Pages (from-to)2556-2563
Number of pages8
JournalInorganic Chemistry
Volume52
Issue number5
DOIs
Publication statusPublished - 4 Mar 2013

Scopus Subject Areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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