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Jan J. Weigand - One of the best experts on this subject based on the ideXlab platform.
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Donor-acceptor interactions in tri(phosphonio)Methanide dications [(Ph3P)2CP(X)Ph2]2+ (X = H, Me, CN, NCS, OH, Cl, OTf, F).
Dalton transactions (Cambridge England : 2003), 2017Co-Authors: Sivathmeehan Yogendra, Felix Hennersdorf, Antonio Bauzá, Antonio Frontera, Roland Fischer, Jan J. WeigandAbstract:The impact of the strongly electron donating carbodiphosphorane moiety in the series of tri(phosphonio)Methanide dications as triflate salts [(Ph3P)2CP(X)Ph2][OTf]2 (X = H, Me, CN, NCS, OH, Cl, OTf, F) deriving from [(Ph3P)2CPPh2][OTf] (19[OTf]) is presented. The influence of the introduced substituents X on the electronic structures of these dications is investigated by means of detailed NBO analysis, NMR spectroscopy and X-ray analysis.
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donor acceptor interactions in tri phosphonio Methanide dications ph3p 2cp x ph2 2 x h me cn ncs oh cl otf f
Dalton Transactions, 2017Co-Authors: Sivathmeehan Yogendra, Felix Hennersdorf, Antonio Bauzá, Antonio Frontera, Roland Fischer, Jan J. WeigandAbstract:The impact of the strongly electron donating carbodiphosphorane moiety in the series of tri(phosphonio)Methanide dications as triflate salts [(Ph3P)2CP(X)Ph2][OTf]2 (X = H, Me, CN, NCS, OH, Cl, OTf, F) deriving from [(Ph3P)2CPPh2][OTf] (19[OTf]) is presented. The influence of the introduced substituents X on the electronic structures of these dications is investigated by means of detailed NBO analysis, NMR spectroscopy and X-ray analysis.
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Reductive Ring Opening of a Cyclo-Tri(phosphonio)Methanide Dication to a Phosphanylcarbodiphosphorane: In Situ UV-Vis Spectroelectrochemistry and Gold Coordination
Organometallics, 2017Co-Authors: Sivathmeehan Yogendra, Felix Hennersdorf, Roland Fischer, Stephen Schulz, Sarath Kumar, Jan J. WeigandAbstract:The formal two-electron reduction of the cyclo-tri(phosphonio)Methanide dication 12+ results in a ring-opening reaction via C–P bond cleavage to yield the unique phosphanyl-functionalized carbodiphosphorane 2. In situ spectroelectrochemical investigations of the reduction of dication 12+ and the oxidation of 2 give insights into the mechanism of this unusual and reversible bond cleavage reaction. Compound 2 features in total three lone pairs of electrons, facilitating the preparation of mono-, di-, and trigold complexes.
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Reductive Ring Opening of a Cyclo-Tri(phosphonio)Methanide Dication to a Phosphanylcarbodiphosphorane: In Situ UV-Vis Spectroelectrochemistry and Gold Coordination
2017Co-Authors: Sivathmeehan Yogendra, Felix Hennersdorf, Roland Fischer, Stephen Schulz, Sarath Kumar, Jan J. WeigandAbstract:The formal two-electron reduction of the cyclo-tri(phosphonio)Methanide dication 12+ results in a ring-opening reaction via C–P bond cleavage to yield the unique phosphanyl-functionalized carbodiphosphorane 2. In situ spectroelectrochemical investigations of the reduction of dication 12+ and the oxidation of 2 give insights into the mechanism of this unusual and reversible bond cleavage reaction. Compound 2 features in total three lone pairs of electrons, facilitating the preparation of mono-, di-, and trigold complexes
Yaofeng Chen - One of the best experts on this subject based on the ideXlab platform.
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Tris(pyrazolyl)Methanide Complexes of Trivalent Rare-Earth Metals
Organometallics, 2016Co-Authors: Guangchao Zhang, Jingjing Guo, Shaowu Wang, Xuebing Leng, Yaofeng ChenAbstract:Three types of trivalent rare-earth-metal complexes supported by a monoanionic tris(pyrazolyl)Methanide ligand were synthesized and structurally characterized, and the catalytic activity of the dialkyl derivatives for isoprene polymerization was investigated. Reactions of the lithium salt of tris(3,5-dimethylpyrazolyl)Methanide LLi(THF) with 1 equiv of ScCl3(THF)3, YCl3, or LuCl3 in THF provided the ion-pair complexes [LLnCl3][Li(THF)4] (Ln = Sc (1), Y (2), Lu (3)). Dialkyl complexes LLn(CH2SiMe3)2(THF) (Ln = Y (4), Lu (5)) were prepared by salt metathesis of LLi(THF) with 1 equiv of [Y(CH2SiMe3)2(THF)3][BPh4] or [Lu(CH2SiMe3)2(THF)3][BPh4] in toluene. Reaction of 5 with PhSiH3 provided the unexpected alkylidene-bridged dinuclear complex L2Lu2(μ-η1:η1-3,5-(CH3)C3HN2)2(μ-CHSiMe3) (6). Complexes 1–6 were structurally characterized by single-crystal X-ray diffraction, showing that the tris(pyrazolyl)Methanide ligand acts as a κ3-coordinating six-electron donor in all complexes. The dialkyl complexes catalyze...
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Tris(pyrazolyl)Methanide Complexes of Trivalent Rare-Earth Metals
2016Co-Authors: Guangchao Zhang, Jingjing Guo, Shaowu Wang, Xuebing Leng, Yaofeng ChenAbstract:Three types of trivalent rare-earth-metal complexes supported by a monoanionic tris(pyrazolyl)Methanide ligand were synthesized and structurally characterized, and the catalytic activity of the dialkyl derivatives for isoprene polymerization was investigated. Reactions of the lithium salt of tris(3,5-dimethylpyrazolyl)Methanide LLi(THF) with 1 equiv of ScCl3(THF)3, YCl3, or LuCl3 in THF provided the ion-pair complexes [LLnCl3][Li(THF)4] (Ln = Sc (1), Y (2), Lu (3)). Dialkyl complexes LLn(CH2SiMe3)2(THF) (Ln = Y (4), Lu (5)) were prepared by salt metathesis of LLi(THF) with 1 equiv of [Y(CH2SiMe3)2(THF)3][BPh4] or [Lu(CH2SiMe3)2(THF)3][BPh4] in toluene. Reaction of 5 with PhSiH3 provided the unexpected alkylidene-bridged dinuclear complex L2Lu2(μ-η1:η1-3,5-(CH3)C3HN2)2(μ-CHSiMe3) (6). Complexes 1–6 were structurally characterized by single-crystal X-ray diffraction, showing that the tris(pyrazolyl)Methanide ligand acts as a κ3-coordinating six-electron donor in all complexes. The dialkyl complexes catalyzed 1,4-cis polymerization of isoprene with high selectivity upon activation with borate and alkylaluminum
Sivathmeehan Yogendra - One of the best experts on this subject based on the ideXlab platform.
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Donor-acceptor interactions in tri(phosphonio)Methanide dications [(Ph3P)2CP(X)Ph2]2+ (X = H, Me, CN, NCS, OH, Cl, OTf, F).
Dalton transactions (Cambridge England : 2003), 2017Co-Authors: Sivathmeehan Yogendra, Felix Hennersdorf, Antonio Bauzá, Antonio Frontera, Roland Fischer, Jan J. WeigandAbstract:The impact of the strongly electron donating carbodiphosphorane moiety in the series of tri(phosphonio)Methanide dications as triflate salts [(Ph3P)2CP(X)Ph2][OTf]2 (X = H, Me, CN, NCS, OH, Cl, OTf, F) deriving from [(Ph3P)2CPPh2][OTf] (19[OTf]) is presented. The influence of the introduced substituents X on the electronic structures of these dications is investigated by means of detailed NBO analysis, NMR spectroscopy and X-ray analysis.
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donor acceptor interactions in tri phosphonio Methanide dications ph3p 2cp x ph2 2 x h me cn ncs oh cl otf f
Dalton Transactions, 2017Co-Authors: Sivathmeehan Yogendra, Felix Hennersdorf, Antonio Bauzá, Antonio Frontera, Roland Fischer, Jan J. WeigandAbstract:The impact of the strongly electron donating carbodiphosphorane moiety in the series of tri(phosphonio)Methanide dications as triflate salts [(Ph3P)2CP(X)Ph2][OTf]2 (X = H, Me, CN, NCS, OH, Cl, OTf, F) deriving from [(Ph3P)2CPPh2][OTf] (19[OTf]) is presented. The influence of the introduced substituents X on the electronic structures of these dications is investigated by means of detailed NBO analysis, NMR spectroscopy and X-ray analysis.
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Reductive Ring Opening of a Cyclo-Tri(phosphonio)Methanide Dication to a Phosphanylcarbodiphosphorane: In Situ UV-Vis Spectroelectrochemistry and Gold Coordination
Organometallics, 2017Co-Authors: Sivathmeehan Yogendra, Felix Hennersdorf, Roland Fischer, Stephen Schulz, Sarath Kumar, Jan J. WeigandAbstract:The formal two-electron reduction of the cyclo-tri(phosphonio)Methanide dication 12+ results in a ring-opening reaction via C–P bond cleavage to yield the unique phosphanyl-functionalized carbodiphosphorane 2. In situ spectroelectrochemical investigations of the reduction of dication 12+ and the oxidation of 2 give insights into the mechanism of this unusual and reversible bond cleavage reaction. Compound 2 features in total three lone pairs of electrons, facilitating the preparation of mono-, di-, and trigold complexes.
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Reductive Ring Opening of a Cyclo-Tri(phosphonio)Methanide Dication to a Phosphanylcarbodiphosphorane: In Situ UV-Vis Spectroelectrochemistry and Gold Coordination
2017Co-Authors: Sivathmeehan Yogendra, Felix Hennersdorf, Roland Fischer, Stephen Schulz, Sarath Kumar, Jan J. WeigandAbstract:The formal two-electron reduction of the cyclo-tri(phosphonio)Methanide dication 12+ results in a ring-opening reaction via C–P bond cleavage to yield the unique phosphanyl-functionalized carbodiphosphorane 2. In situ spectroelectrochemical investigations of the reduction of dication 12+ and the oxidation of 2 give insights into the mechanism of this unusual and reversible bond cleavage reaction. Compound 2 features in total three lone pairs of electrons, facilitating the preparation of mono-, di-, and trigold complexes
Peter W. Roesky - One of the best experts on this subject based on the ideXlab platform.
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(Iminophosphoranyl)(thiophosphoranyl)Methanide {CH(PPh2NSiMe3)(Ph2PS)}− as a Ligand in Rare-Earth-Element Chemistry
Organometallics, 2013Co-Authors: Balasubramanian Murugesapandian, Magdalena Kuzdrowska, Michael T. Gamer, Larissa Hartenstein, Peter W. RoeskyAbstract:The (iminophosphoranyl)(thiophosphoranyl)Methanide {CH(PPh2═NSiMe3)(PPh2═S)}− has been introduced as a ligand into the chemistry of yttrium and the lanthanides. First, the bimetallic potassium reag...
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iminophosphoranyl thiophosphoranyl Methanide ch pph2nsime3 ph2ps as a ligand in rare earth element chemistry
Organometallics, 2013Co-Authors: Balasubramanian Murugesapandian, Magdalena Kuzdrowska, Michael T. Gamer, Larissa Hartenstein, Peter W. RoeskyAbstract:The (iminophosphoranyl)(thiophosphoranyl)Methanide {CH(PPh2═NSiMe3)(PPh2═S)}− has been introduced as a ligand into the chemistry of yttrium and the lanthanides. First, the bimetallic potassium reag...
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a well defined silica supported lanthanum bis phosphinimino Methanide
European Journal of Inorganic Chemistry, 2011Co-Authors: Bertrand Revel, Peter W. Roesky, Laurent Delevoye, Grégory Tricot, Marcus Rastätter, Magdalena Kuzdrowska, Régis M. GauvinAbstract:Grafting of the bis(phosphinimino)Methanide complex [La{CH(PPh2NSiMe3)2}{N(SiHMe2)2}2] (1) onto dehydroxylated silica (SiO2-700) affords material 2. Full characterization of this material by infrared spectroscopy, elemental analysis, and multinuclear, multidimensional solid-state NMR spectroscopy showed formation of well-defined bis(phosphinimino)Methanide amido surface species, [(≡SiO)La{CH(PPh2NSiMe3)2}{N(SiHMe2)2}], along with [≡SiOSiHMe2] sites.
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A Well‐Defined Silica‐Supported Lanthanum Bis(phosphinimino)Methanide
European Journal of Inorganic Chemistry, 2011Co-Authors: Bertrand Revel, Peter W. Roesky, Laurent Delevoye, Grégory Tricot, Marcus Rastätter, Magdalena Kuzdrowska, Régis M. GauvinAbstract:Grafting of the bis(phosphinimino)Methanide complex [La{CH(PPh2NSiMe3)2}{N(SiHMe2)2}2] (1) onto dehydroxylated silica (SiO2-700) affords material 2. Full characterization of this material by infrared spectroscopy, elemental analysis, and multinuclear, multidimensional solid-state NMR spectroscopy showed formation of well-defined bis(phosphinimino)Methanide amido surface species, [(≡SiO)La{CH(PPh2NSiMe3)2}{N(SiHMe2)2}], along with [≡SiOSiHMe2] sites.
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Main-group and transition-metal complexes of bis(phosphinimino)Methanides
Chemical Society reviews, 2009Co-Authors: Tarun K. Panda, Peter W. RoeskyAbstract:Bis(phosphinimino)Methanides exhibit a wide variety of coordination chemistry with almost all elements in the periodic table. This critical review deals with the chemistry and coordination behavior of bulky monoanionic {CH(PPh2NR)2}− bis(phosphinimino)Methanide and dianionic {C(PPh2NR)2}2− bis(phosphinimino)methanediide (R = SiMe3, aryl) ligands focusing on s- and p-block as well as transition metals (109 references).
Guangchao Zhang - One of the best experts on this subject based on the ideXlab platform.
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Tris(pyrazolyl)Methanide Complexes of Trivalent Rare-Earth Metals
Organometallics, 2016Co-Authors: Guangchao Zhang, Jingjing Guo, Shaowu Wang, Xuebing Leng, Yaofeng ChenAbstract:Three types of trivalent rare-earth-metal complexes supported by a monoanionic tris(pyrazolyl)Methanide ligand were synthesized and structurally characterized, and the catalytic activity of the dialkyl derivatives for isoprene polymerization was investigated. Reactions of the lithium salt of tris(3,5-dimethylpyrazolyl)Methanide LLi(THF) with 1 equiv of ScCl3(THF)3, YCl3, or LuCl3 in THF provided the ion-pair complexes [LLnCl3][Li(THF)4] (Ln = Sc (1), Y (2), Lu (3)). Dialkyl complexes LLn(CH2SiMe3)2(THF) (Ln = Y (4), Lu (5)) were prepared by salt metathesis of LLi(THF) with 1 equiv of [Y(CH2SiMe3)2(THF)3][BPh4] or [Lu(CH2SiMe3)2(THF)3][BPh4] in toluene. Reaction of 5 with PhSiH3 provided the unexpected alkylidene-bridged dinuclear complex L2Lu2(μ-η1:η1-3,5-(CH3)C3HN2)2(μ-CHSiMe3) (6). Complexes 1–6 were structurally characterized by single-crystal X-ray diffraction, showing that the tris(pyrazolyl)Methanide ligand acts as a κ3-coordinating six-electron donor in all complexes. The dialkyl complexes catalyze...
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Tris(pyrazolyl)Methanide Complexes of Trivalent Rare-Earth Metals
2016Co-Authors: Guangchao Zhang, Jingjing Guo, Shaowu Wang, Xuebing Leng, Yaofeng ChenAbstract:Three types of trivalent rare-earth-metal complexes supported by a monoanionic tris(pyrazolyl)Methanide ligand were synthesized and structurally characterized, and the catalytic activity of the dialkyl derivatives for isoprene polymerization was investigated. Reactions of the lithium salt of tris(3,5-dimethylpyrazolyl)Methanide LLi(THF) with 1 equiv of ScCl3(THF)3, YCl3, or LuCl3 in THF provided the ion-pair complexes [LLnCl3][Li(THF)4] (Ln = Sc (1), Y (2), Lu (3)). Dialkyl complexes LLn(CH2SiMe3)2(THF) (Ln = Y (4), Lu (5)) were prepared by salt metathesis of LLi(THF) with 1 equiv of [Y(CH2SiMe3)2(THF)3][BPh4] or [Lu(CH2SiMe3)2(THF)3][BPh4] in toluene. Reaction of 5 with PhSiH3 provided the unexpected alkylidene-bridged dinuclear complex L2Lu2(μ-η1:η1-3,5-(CH3)C3HN2)2(μ-CHSiMe3) (6). Complexes 1–6 were structurally characterized by single-crystal X-ray diffraction, showing that the tris(pyrazolyl)Methanide ligand acts as a κ3-coordinating six-electron donor in all complexes. The dialkyl complexes catalyzed 1,4-cis polymerization of isoprene with high selectivity upon activation with borate and alkylaluminum