Document Type

Journal Article

Department/Unit

Department of Chemistry

Title

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

Language

English

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. © 2013 American Chemical Society.

Publication Date

2013

Source Publication Title

Inorganic Chemistry

Volume

52

Issue

5

Start Page

2556

End Page

2563

Publisher

American Chemical Society

DOI

10.1021/ic302567e

Link to Publisher's Edition

http://dx.doi.org/10.1021/ic302567e

ISSN (print)

00201669

ISSN (electronic)

1520510X

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