Heterometallic Cerium(IV) Perrhenate, Permanganate, and Molybdate Complexes Supported by the Imidodiphosphinate Ligand [N(i‑Pr2PO)2]−

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-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–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-Pr2­PO)2}3]2­(μ-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 3–6 have been determined.