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Gregory H Robinson - One of the best experts on this subject based on the ideXlab platform.
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protonation of carbene stabilized Diphosphorus complexation of hp2
Chemical Communications, 2016Co-Authors: Yuzhong Wang, Henry F Schaefer, Hunter P Hickox, Melody R Walter, Gregory H RobinsonAbstract:Reaction of carbene-stabilized Diphosphorus, L:P–P:L (5) (L: = :C{N(2,6-Pri2C6H3)CH}2) with pyridine hydrochloride yields [L:(H)P–P:L]Cl (6), a salt containing the HP2+ cation—the elusive phosphorus analogue of the well known diazonium cation, HN2+. In addition to reporting the synthesis and structure, the nature of (6) was further probed by DFT computations. Interestingly, carbenes may be employed to deprotonate (6), affording the starting material (5).
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splitting molecular oxygen en route to a stable molecule containing Diphosphorus tetroxide
Journal of the American Chemical Society, 2013Co-Authors: Yuzhong Wang, Henry F Schaefer, Paul V R Schleyer, Gregory H RobinsonAbstract:In contrast to stable phosphorus oxides such as P4O6 and P4O10 that possess iconic adamantane-like cage structures, highly reactive phosphorus oxides such as PO, PO2, and P2Ox (x = 1–5) only have been studied in the gas phase or by matrix isolation techniques. Elusive Diphosphorus tetroxide, the long sought phosphorus analogue of N2O4, is particularly noteworthy. Computations predict that the oxo-bridged O2POPO form of P2O4 is energetically more favored than the P–P bonded O2P–PO2 isomer. Herein, we report the experimental realization of Diphosphorus tetroxide—in its energetically disfavored O2P–PO2 form—via carbene-stabilization. The synthesis of the title compound involves the splitting of molecular oxygen by carbene-stabilized Diphosphorus.
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carbene stabilized Diphosphorus bidentate complexation of bh2
Chemical Communications, 2011Co-Authors: Yuzhong Wang, Henry F Schaefer, Mariham Y Abraham, Paul Von Rague Schleyer, Gregory H RobinsonAbstract:Reaction of carbene-stabilized Diphosphorus, L:P–P:L (L: = :C{N(2,6-Pri2C6H3)CH}2, 1), with excess BH3·THF affords the boronium salt [L:P(μ-BH2)P:L]+[B2H7]−, 2, which contains a three-membered P2B ring. When 2 is dissolved in THF, compounds 1 and 2 exist in a dynamic solution equilibrium.
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Carbene-stabilized Diphosphorus: bidentate complexation of BH2(+).
Chemical Communications, 2011Co-Authors: Yuzhong Wang, Henry F Schaefer, Mariham Y Abraham, Paul Von Rague Schleyer, Gregory H RobinsonAbstract:Reaction of carbene-stabilized Diphosphorus, L:P–P:L (L: = :C{N(2,6-Pri2C6H3)CH}2, 1), with excess BH3·THF affords the boronium salt [L:P(μ-BH2)P:L]+[B2H7]−, 2, which contains a three-membered P2B ring. When 2 is dissolved in THF, compounds 1 and 2 exist in a dynamic solution equilibrium.
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Carbene-Stabilized Parent Phosphinidene†
Organometallics, 2010Co-Authors: Yuzhong Wang, Henry F Schaefer, Paul V R Schleyer, Mariham Y Abraham, Robert J. Gilliard, Gregory H RobinsonAbstract:The lithiated N-heterocyclic carbene−phosphinidene adduct L′:P−H (3; L′: = :C{[N(2,6-Pri2C6H3)]2CHCLi(THF)3}) unexpectedly resulted from the reaction of lithium metal with the carbene-stabilized Diphosphorus species L:P−P:L (2; L: = :C{N(2,6-Pri2C6H3)CH}2). Compound 2 was previously prepared by the potassium graphite reduction of L:PCl3 (1).
Yuzhong Wang - One of the best experts on this subject based on the ideXlab platform.
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protonation of carbene stabilized Diphosphorus complexation of hp2
Chemical Communications, 2016Co-Authors: Yuzhong Wang, Henry F Schaefer, Hunter P Hickox, Melody R Walter, Gregory H RobinsonAbstract:Reaction of carbene-stabilized Diphosphorus, L:P–P:L (5) (L: = :C{N(2,6-Pri2C6H3)CH}2) with pyridine hydrochloride yields [L:(H)P–P:L]Cl (6), a salt containing the HP2+ cation—the elusive phosphorus analogue of the well known diazonium cation, HN2+. In addition to reporting the synthesis and structure, the nature of (6) was further probed by DFT computations. Interestingly, carbenes may be employed to deprotonate (6), affording the starting material (5).
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splitting molecular oxygen en route to a stable molecule containing Diphosphorus tetroxide
Journal of the American Chemical Society, 2013Co-Authors: Yuzhong Wang, Henry F Schaefer, Paul V R Schleyer, Gregory H RobinsonAbstract:In contrast to stable phosphorus oxides such as P4O6 and P4O10 that possess iconic adamantane-like cage structures, highly reactive phosphorus oxides such as PO, PO2, and P2Ox (x = 1–5) only have been studied in the gas phase or by matrix isolation techniques. Elusive Diphosphorus tetroxide, the long sought phosphorus analogue of N2O4, is particularly noteworthy. Computations predict that the oxo-bridged O2POPO form of P2O4 is energetically more favored than the P–P bonded O2P–PO2 isomer. Herein, we report the experimental realization of Diphosphorus tetroxide—in its energetically disfavored O2P–PO2 form—via carbene-stabilization. The synthesis of the title compound involves the splitting of molecular oxygen by carbene-stabilized Diphosphorus.
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carbene stabilized Diphosphorus bidentate complexation of bh2
Chemical Communications, 2011Co-Authors: Yuzhong Wang, Henry F Schaefer, Mariham Y Abraham, Paul Von Rague Schleyer, Gregory H RobinsonAbstract:Reaction of carbene-stabilized Diphosphorus, L:P–P:L (L: = :C{N(2,6-Pri2C6H3)CH}2, 1), with excess BH3·THF affords the boronium salt [L:P(μ-BH2)P:L]+[B2H7]−, 2, which contains a three-membered P2B ring. When 2 is dissolved in THF, compounds 1 and 2 exist in a dynamic solution equilibrium.
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Carbene-stabilized Diphosphorus: bidentate complexation of BH2(+).
Chemical Communications, 2011Co-Authors: Yuzhong Wang, Henry F Schaefer, Mariham Y Abraham, Paul Von Rague Schleyer, Gregory H RobinsonAbstract:Reaction of carbene-stabilized Diphosphorus, L:P–P:L (L: = :C{N(2,6-Pri2C6H3)CH}2, 1), with excess BH3·THF affords the boronium salt [L:P(μ-BH2)P:L]+[B2H7]−, 2, which contains a three-membered P2B ring. When 2 is dissolved in THF, compounds 1 and 2 exist in a dynamic solution equilibrium.
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Carbene-Stabilized Parent Phosphinidene†
Organometallics, 2010Co-Authors: Yuzhong Wang, Henry F Schaefer, Paul V R Schleyer, Mariham Y Abraham, Robert J. Gilliard, Gregory H RobinsonAbstract:The lithiated N-heterocyclic carbene−phosphinidene adduct L′:P−H (3; L′: = :C{[N(2,6-Pri2C6H3)]2CHCLi(THF)3}) unexpectedly resulted from the reaction of lithium metal with the carbene-stabilized Diphosphorus species L:P−P:L (2; L: = :C{N(2,6-Pri2C6H3)CH}2). Compound 2 was previously prepared by the potassium graphite reduction of L:PCl3 (1).
Henry F Schaefer - One of the best experts on this subject based on the ideXlab platform.
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protonation of carbene stabilized Diphosphorus complexation of hp2
Chemical Communications, 2016Co-Authors: Yuzhong Wang, Henry F Schaefer, Hunter P Hickox, Melody R Walter, Gregory H RobinsonAbstract:Reaction of carbene-stabilized Diphosphorus, L:P–P:L (5) (L: = :C{N(2,6-Pri2C6H3)CH}2) with pyridine hydrochloride yields [L:(H)P–P:L]Cl (6), a salt containing the HP2+ cation—the elusive phosphorus analogue of the well known diazonium cation, HN2+. In addition to reporting the synthesis and structure, the nature of (6) was further probed by DFT computations. Interestingly, carbenes may be employed to deprotonate (6), affording the starting material (5).
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splitting molecular oxygen en route to a stable molecule containing Diphosphorus tetroxide
Journal of the American Chemical Society, 2013Co-Authors: Yuzhong Wang, Henry F Schaefer, Paul V R Schleyer, Gregory H RobinsonAbstract:In contrast to stable phosphorus oxides such as P4O6 and P4O10 that possess iconic adamantane-like cage structures, highly reactive phosphorus oxides such as PO, PO2, and P2Ox (x = 1–5) only have been studied in the gas phase or by matrix isolation techniques. Elusive Diphosphorus tetroxide, the long sought phosphorus analogue of N2O4, is particularly noteworthy. Computations predict that the oxo-bridged O2POPO form of P2O4 is energetically more favored than the P–P bonded O2P–PO2 isomer. Herein, we report the experimental realization of Diphosphorus tetroxide—in its energetically disfavored O2P–PO2 form—via carbene-stabilization. The synthesis of the title compound involves the splitting of molecular oxygen by carbene-stabilized Diphosphorus.
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carbene stabilized Diphosphorus bidentate complexation of bh2
Chemical Communications, 2011Co-Authors: Yuzhong Wang, Henry F Schaefer, Mariham Y Abraham, Paul Von Rague Schleyer, Gregory H RobinsonAbstract:Reaction of carbene-stabilized Diphosphorus, L:P–P:L (L: = :C{N(2,6-Pri2C6H3)CH}2, 1), with excess BH3·THF affords the boronium salt [L:P(μ-BH2)P:L]+[B2H7]−, 2, which contains a three-membered P2B ring. When 2 is dissolved in THF, compounds 1 and 2 exist in a dynamic solution equilibrium.
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Carbene-stabilized Diphosphorus: bidentate complexation of BH2(+).
Chemical Communications, 2011Co-Authors: Yuzhong Wang, Henry F Schaefer, Mariham Y Abraham, Paul Von Rague Schleyer, Gregory H RobinsonAbstract:Reaction of carbene-stabilized Diphosphorus, L:P–P:L (L: = :C{N(2,6-Pri2C6H3)CH}2, 1), with excess BH3·THF affords the boronium salt [L:P(μ-BH2)P:L]+[B2H7]−, 2, which contains a three-membered P2B ring. When 2 is dissolved in THF, compounds 1 and 2 exist in a dynamic solution equilibrium.
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Carbene-Stabilized Parent Phosphinidene†
Organometallics, 2010Co-Authors: Yuzhong Wang, Henry F Schaefer, Paul V R Schleyer, Mariham Y Abraham, Robert J. Gilliard, Gregory H RobinsonAbstract:The lithiated N-heterocyclic carbene−phosphinidene adduct L′:P−H (3; L′: = :C{[N(2,6-Pri2C6H3)]2CHCLi(THF)3}) unexpectedly resulted from the reaction of lithium metal with the carbene-stabilized Diphosphorus species L:P−P:L (2; L: = :C{N(2,6-Pri2C6H3)CH}2). Compound 2 was previously prepared by the potassium graphite reduction of L:PCl3 (1).
Jan J Weigand - One of the best experts on this subject based on the ideXlab platform.
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preparation of ligand stabilized p4o4 2 by controlled hydrolysis of a janus head type Diphosphorus trication
Angewandte Chemie, 2010Co-Authors: Jan J Weigand, Kaioliver Feldmann, Antje K C Echterhoff, Andreas W Ehlers, Koop LammertsmaAbstract:A door to new opportunities: The stepwise hydrolysis of a Diphosphorus trication is an efficient method for the preparation of an unusual ligand-stabilized dication that contains a novel cationic [P4O4]2+ framework (see Scheme; gray C, blue N, red O, orange P). This approach demonstrates the potential of the Diphosphorus trication as a source for phosphorus building blocks to be used in the construction of novel cationic ring and cluster systems. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Preparation of Ligand‐Stabilized [P4O4]2+ by Controlled Hydrolysis of a Janus Head Type Diphosphorus Trication
Angewandte Chemie, 2010Co-Authors: Jan J Weigand, Antje K C Echterhoff, Andreas W Ehlers, Kai‐oliver Feldmann, Koop LammertsmaAbstract:A door to new opportunities: The stepwise hydrolysis of a Diphosphorus trication is an efficient method for the preparation of an unusual ligand-stabilized dication that contains a novel cationic [P4O4]2+ framework (see Scheme; gray C, blue N, red O, orange P). This approach demonstrates the potential of the Diphosphorus trication as a source for phosphorus building blocks to be used in the construction of novel cationic ring and cluster systems. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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bifunctional Diphosphorus lewis acids from cyclodiphosphadiazanes
Chemical Communications, 2007Co-Authors: Reagan J Davidson, Jan J Weigand, Neil Burford, Stanley T Cameron, Andreas Decken, Ulrike WernerzwanzigerAbstract:The quantitative displacement of triflate groups in 1,3-ditriflato-2,4-bis(2,6-dimethylphenyl)cyclodiphospha-2,4-diazane by DMAP (4-dimethylaminopyridine) or Me3P gives dicationic complexes containing bifunctional Diphosphorus Lewis acceptors.
Manfred Scheer - One of the best experts on this subject based on the ideXlab platform.
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the potential of the Diphosphorus complex cp2w2 co 4 η2 p2 as an organometallic connecter in supramolecular chemistry
European Journal of Inorganic Chemistry, 2019Co-Authors: Mehdi Elsayed Moussa, Pavel A Shelyganov, Brian Wegley, Michael Seidl, Manfred ScheerAbstract:: For the first time, the tetrahedral Diphosphorus complex [Cp2W2(CO)4(µ,η2:η2-P2)] (Cp = C5H5) (3) is used as a connecter in supramolecular chemistry. The treatment of 3 with CuI halides leads to the formation of the new one-dimensional (1D) linear polymers [Cu(µ-X){Cp2W2(CO)4(µ,η2:η2:η1:η1-P2)}] n {X = Cl (4), Br (5), I (6)}. The coordination polymers (CPs) 4-6 are almost insoluble in organic solvents, thus, their 31P MAS-NMR spectra were recorded and found to be remarkably influenced by their solid-state structures. Additionally, we demonstrate that by reacting the Cp-substituted Diphosphorus complex [Cp'2W2(CO)4(µ,η2:η2-P2)] {Cp' = C5H4{C(CH3)3}} (7) with CuBr, the unprecedented soluble 1D CP [Cu(µ-Br){Cp'2W2(CO)4(µ,η2:η2:η1:η1-P2)}] n (8) is obtained. Furthermore, the reactions of 3 with the AgI salts Ag[CF3SO3] and Ag[PF6] result in the formation of the oligomeric dicationic species [Ag2{Cp2W2(CO)4(µ,η2:η2:η2-P2)}2 {Cp2W2(CO)4(µ,η2:η2:η1:η1-P2)}2][X']2 {X' = [CF3SO3]- (9), [PF6]- (10)}.
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the Diphosphorus complex cp2cr2 co 4 η2 p2 as a building block in the coordination chemistry of silver
European Journal of Inorganic Chemistry, 2018Co-Authors: Medhi Elsayed Moussa, Gabor Balazs, Michael Seidl, Stephan Welsch, Laurence J Gregoriades, Manfred ScheerAbstract:The reaction of the tetrahedral Diphosphorus complex [Cp2Cr2(CO)4(η2‐P2)] (Cp = C5H5) (2) with Ag[Al{OC(CF3)3}4] (AgTEF) (3) leads to the formation of the AgI dimer [Ag2(η2‐2) (η1‐2)(η1:η1‐2)2][TEF]2 (5). This dimer can be used as a suitable precursor for the synthesis of the unprecedented 1D organometallic‐organic hybrid polymer [Ag2(η1‐2)2(η1:η1‐2)2{µ,η1:η1‐(C8H4N2)}]n[TEF]2n (8) upon its reaction with 1,4‐dicyanobenzene (7). The driving force for this supramolecular assembly reaction is supported by DFT calculations.
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The Diphosphorus Complex [Cp2Cr2(CO)4(η2-P2)] as a Building Block in the Coordination Chemistry of Silver: The Diphosphorus Complex [Cp2Cr2(CO)4(η2-P2)] as a Building Block in the Coordination Chemistry of Silver
European Journal of Inorganic Chemistry, 2018Co-Authors: Medhi Elsayed Moussa, Gabor Balazs, Michael Seidl, Stephan Welsch, Laurence J Gregoriades, Manfred ScheerAbstract:The reaction of the tetrahedral Diphosphorus complex [Cp2Cr2(CO)4(η2‐P2)] (Cp = C5H5) (2) with Ag[Al{OC(CF3)3}4] (AgTEF) (3) leads to the formation of the AgI dimer [Ag2(η2‐2) (η1‐2)(η1:η1‐2)2][TEF]2 (5). This dimer can be used as a suitable precursor for the synthesis of the unprecedented 1D organometallic‐organic hybrid polymer [Ag2(η1‐2)2(η1:η1‐2)2{µ,η1:η1‐(C8H4N2)}]n[TEF]2n (8) upon its reaction with 1,4‐dicyanobenzene (7). The driving force for this supramolecular assembly reaction is supported by DFT calculations.
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preorganized agi bimetallic precursor with labile Diphosphorus ligands for a programmed synthesis of organometallic organic hybrid polymers
Chemistry: A European Journal, 2017Co-Authors: Mehdi Elsayed Moussa, Bianca Attenberger, Gabor Balazs, Michael Seidl, Manfred Zabel, Alexander V Virovets, Andrea Schreiner, Manfred ScheerAbstract:An AgI dimer capped with labile organometallic Diphosphorus ligands [Cp2Mo2(CO)4(η2-P2)] (Cp=C5H5) acts as a highly pre-organized molecular precursor to direct the construction of 1D or 2D, and 3D organometallic–organic hybrid coordination polymers upon reaction with ditopic pyridine-based linkers. The formation of the supramolecular aggregates can be controlled by the stoichiometry of the organic molecules, and the mechanism is supported by DFT calculations.
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Preorganized AgI Bimetallic Precursor with Labile Diphosphorus Ligands for a Programmed Synthesis of Organometallic–Organic Hybrid Polymers
Chemistry: A European Journal, 2017Co-Authors: Mehdi Elsayed Moussa, Bianca Attenberger, Gabor Balazs, Michael Seidl, Manfred Zabel, Alexander V Virovets, Andrea Schreiner, Manfred ScheerAbstract:An AgI dimer capped with labile organometallic Diphosphorus ligands [Cp2Mo2(CO)4(η2-P2)] (Cp=C5H5) acts as a highly pre-organized molecular precursor to direct the construction of 1D or 2D, and 3D organometallic–organic hybrid coordination polymers upon reaction with ditopic pyridine-based linkers. The formation of the supramolecular aggregates can be controlled by the stoichiometry of the organic molecules, and the mechanism is supported by DFT calculations.