Preparation and Characterization of Dinuclear NiII Amine‐Thiophenolate Complexes Coligated by EO4– (E = Cl, Re) and EO42– Oxoanions (E = S, Cr, Mo, W)

Lozan, Vasile; Kersting, Berthold

doi:10.1002/ejic.200700015

Cited by 17 publications

(24 citation statements)

References 23 publications

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“…The ligand K[N( i -Pr 2 PO) 2 ] was prepared according to a literature method. The compounds Ce[N( i -Pr 2 PO) 2 ] 3 Cl ( 1 ), AgReO 4 , AgMnO 4 , ( n -Bu 4 N) 2 [MoO 4 ], and ( n -Bu 4 N)[Cp*MoO 3 ] (Cp* = η 5 -C 5 Me 5 ) were synthesized as described elsewhere. All other reagents were purchased from commercial sources and used as received.…”

Section: Methodsmentioning

confidence: 99%

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

et al. 2013

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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.

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Section: Methodsmentioning

confidence: 99%

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

et al. 2013

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“…More recent examples of metalated container molecules are 20-22 with classical [65,66] or organometallic metallo coligands (Scheme 1.4) [64]. Such compounds Scheme 1.3 Exchange of carboxylate ligands in dizinc complexes 14.…”

Section: Variation Coordination Modes and Activation Of Coligandsmentioning

confidence: 99%

“…are readily accessible from the labile ClO 4 À complexes 19a,b [65]. They are stable in a range of organic solvents, and their charged nature gives them good solubility.…”

Section: Metalated Container Molecules Of Binucleating Supporting Ligmentioning

confidence: 99%

Chemistry of Metalated Container Molecules

Kersting

2009

Activating Unreactive Substrates

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“…[14] In previous work, we described a series of dinuclear transition-metal complexes of the macrocyclic N 6 S 2 ligands L 1 and L 2 (Scheme 1). [15,16] These complexes have a rich coordination chemistry since the [L 1 M 2 ] 2+ fragments are able to coordinate a large variety of coligands such as Cl -, [15] OH -, [17] NO 2 -, NO 3 -, N 3 -, [18] BH 4 -, [19] ClO 4 -, ReO 4 -, SO 4 2-, MoO 4 2-, [20] MoO 3 (OMe) -, [21] and various carboxylate anions. [16,22,23] The magnetic properties of an isostructural series of bioctahedral [L 1 M II 2 (OAc)] + complexes have also been reported.…”

Section: Introductionmentioning

confidence: 99%

Tetranuclear Nickel Complexes Composed of Pairs of Dinuclear LNi₂ Fragments Linked by 4,4′‐Bipyrazolyl, 1,4‐Bis(4′‐pyrazolyl)benzene, and 4,4′‐Bipyridazine: Synthesis, Structures, and Magnetic Properties

et al. 2007

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The ability of the ligands 4,4′‐bipyrazolyl (H2bpz), 1,4‐bis(4′‐pyrazolyl)benzene (H2bpzb), and 4,4′‐bipyridazine (bpdz) to link two dioctahedral LNi2 units has been examined. Thefollowing complexes were prepared: [L1NiII2(Hbpz)][BPh4] (6[BPh4]), [L1NiII2(bpdz)][ClO4]2 (7[ClO4]2), [(L1NiII2)2(bpzb)][BPh4]2 (8[BPh4]2), and [(L2NiII2)2(bpz)][BPh4]2 (9[BPh4]2), where (L1)2– and (L2)2– represent macrocyclic hexaaza‐dithiophenolate ligands. All complexes have been characterised by UV/Vis spectroscopy, IR spectroscopy, and X‐ray crystallography. Whereas (Hbpz)– and bpdz in 6[BPh4]2 and 7[ClO4]2 act as bidentate ligands coordinating to only one [LNi2]2+ unit, in 8[BPh4]2 and 9[BPh4]2 the (bpzb)2– and(bpz)2– units are tetradentate linkers. This is qualitatively explained in terms of the absence or presence of steric repulsions between the tBu groups of the supporting ligands and the length of the coligands. The structures of the tetranuclear complexes differ mainly in the distance between the center of the Ni···Ni axes of the isostructural [LNi2] units {14.040(1) Å in 8[BPh4]2, 9.184(1) Å in 9[BPh4]2}. The two Ni2pyrazolato planes in 9[BPh4]2 are coplanar. An analysis of the temperature‐dependent magnetic susceptibility data for 9[BPh4]2 reveals the presence of weak ferromagnetic exchange interactions between the NiII ions in the binuclear [L2Ni2] subunits with values for the magnetic exchange constant J1 of 23.97 cm–1 (H = –2JS1S2). The exchange coupling across the dipyrazolato bridge is less than 0.1 cm–1, suggesting that no significant interdimer exchange coupling occurs in 9[BPh4]2. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Preparation and Characterization of Dinuclear Ni^II Amine‐Thiophenolate Complexes Coligated by EO₄^– (E = Cl, Re) and EO₄^2– Oxoanions (E = S, Cr, Mo, W)

Cited by 17 publications

References 23 publications

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 Supported by the Imidodiphosphinate Ligand [N(i-Pr₂PO)₂]⁻

Chemistry of Metalated Container Molecules

Tetranuclear Nickel Complexes Composed of Pairs of Dinuclear LNi₂ Fragments Linked by 4,4′‐Bipyrazolyl, 1,4‐Bis(4′‐pyrazolyl)benzene, and 4,4′‐Bipyridazine: Synthesis, Structures, and Magnetic Properties

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Preparation and Characterization of Dinuclear NiII Amine‐Thiophenolate Complexes Coligated by EO4– (E = Cl, Re) and EO42– Oxoanions (E = S, Cr, Mo, W)

Cited by 17 publications

References 23 publications

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 Supported by the Imidodiphosphinate Ligand [N(i-Pr2PO)2]−

Chemistry of Metalated Container Molecules

Tetranuclear Nickel Complexes Composed of Pairs of Dinuclear LNi2 Fragments Linked by 4,4′‐Bipyrazolyl, 1,4‐Bis(4′‐pyrazolyl)benzene, and 4,4′‐Bipyridazine: Synthesis, Structures, and Magnetic Properties

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Preparation and Characterization of Dinuclear Ni^II Amine‐Thiophenolate Complexes Coligated by EO₄^– (E = Cl, Re) and EO₄^2– Oxoanions (E = S, Cr, Mo, W)

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 Supported by the Imidodiphosphinate Ligand [N(i-Pr₂PO)₂]⁻

Tetranuclear Nickel Complexes Composed of Pairs of Dinuclear LNi₂ Fragments Linked by 4,4′‐Bipyrazolyl, 1,4‐Bis(4′‐pyrazolyl)benzene, and 4,4′‐Bipyridazine: Synthesis, Structures, and Magnetic Properties