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

doi:10.1021/ic302567e

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

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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 language	English
Pages (from-to)	2556-2563
Number of pages	8
Journal	Inorganic Chemistry
Volume	52
Issue number	5
DOIs	https://doi.org/10.1021/ic302567e
Publication status	Published - 4 Mar 2013
Externally published	Yes

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@article{9b227f1cb7e7422e8b30bca090cf8cca,

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-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) {\AA}] 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.",

author = "Wang, {Guo Cang} and Sung, {Herman H.Y.} and Dai, {Feng Rong} and Chiu, {Wai Hang} and Wong, {Wai Yeung} and Williams, {Ian D.} and Leung, {Wa Hung}",

year = "2013",

month = mar,

day = "4",

doi = "10.1021/ic302567e",

language = "English",

volume = "52",

pages = "2556--2563",

number = "5",

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TY - JOUR

T1 - Heterometallic cerium(IV) perrhenate, permanganate, and molybdate complexes supported by the imidodiphosphinate ligand [N(i -Pr2PO) 2]-

AU - Wang, Guo Cang

AU - Sung, Herman H.Y.

AU - Dai, Feng Rong

AU - Chiu, Wai Hang

AU - Wong, Wai Yeung

AU - Williams, Ian D.

AU - Leung, Wa Hung

PY - 2013/3/4

Y1 - 2013/3/4

N2 - 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.

AB - 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.

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U2 - 10.1021/ic302567e

DO - 10.1021/ic302567e

M3 - Article

AN - SCOPUS:84874587899

SN - 0020-1669

VL - 52

SP - 2556

EP - 2563

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 5

ER -

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

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