title: Heterometallic cerium(IV) perrhenate, permanganate, and molybdate complexes supported by the imidodiphosphinate ligand [N(i-Pr2PO)2]-.
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-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.
authors: Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, People's Republic of China.
authors: Guo-Cang
authors: GC
authors: Wang
authors: Herman H Y
authors: HH
authors: Sung
authors: Feng-Rong
authors: FR
authors: Dai
authors: Wai-Hang
authors: WH
authors: Chiu
authors: Wai-Yeung
authors: WY
authors: Wong
authors: Ian D
authors: ID
authors: Williams
authors: Wa-Hung
authors: WH
authors: Leung
mesh_terms: D002563:Cerium / Q000737:chemistry*; D007094:Imides / Q000737:chemistry; D017895:Manganese Compounds / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010087:Oxides / Q000737:chemistry*; D010721:Phosphinic Acids / Q000737:chemistry*; D012211:Rhenium / Q000737:chemistry*
chemical_list: D007094:Imides; D017895:Manganese Compounds; D009942:Organometallic Compounds; D010087:Oxides; D010721:Phosphinic Acids; C048856:permanganic acid; C015428:perrhenate; D002563:Cerium; D012211:Rhenium; D008982:Molybdenum