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Miguel A. Esteruelas - One of the best experts on this subject based on the ideXlab platform.
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Elongated σ-Borane versus σ-Borane in Pincer–POP–Osmium Complexes
Organometallics, 2017Co-Authors: Miguel A. Esteruelas, Israel Fernández, Cristina García-yebra, Jaime Martín, Enrique OñateAbstract:Square pyramidal metal fragments OsHX{κ3-P,O,P-[xant(PiPr2)2]} (X = Cl, H; xant(PiPr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphine)xanthene) coordinate the B–H bond of Boranes trans to the ligand X. As a consequence, elongated σ-Borane and σ-Borane pincer–POP–osmium complexes have been isolated and fully characterized. The interaction between the metal fragment and the coordinated B–H has been analyzed as a function of X, from spectroscopic, X-ray diffraction, and theoretical points of view. The dinuclear complex [(Os(H···H){κ3-P,O,P-[xant(PiPr2)2]})2(μ-Cl)2][BF4]2 (3) reacts with catecholBorane (HBcat) and pinacolBorane (HBpin) to give the elongated σ-Borane Derivative OsHCl(η2-H-BR2){κ3-P,O,P-[xant(PiPr2)2]} (BR2 = Bcat (4) and Bpin (5)), as well as H2, FBR2, and BF3. The elongated σ-Borane character of 4 and 5 is supported by X-ray diffraction analysis and DFT-optimized structures of both compounds, which show distances between the coordinated B and H atoms of the Borane in the range of 1.6–1.7 A. AIM...
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Elongated σ‑Borane versus σ‑Borane in Pincer–POP–Osmium Complexes
2017Co-Authors: Miguel A. Esteruelas, Israel Fernández, Cristina García-yebra, Jaime Martín, Enrique OñateAbstract:Square pyramidal metal fragments OsHX{κ3-P,O,P-[xant(PiPr2)2]} (X = Cl, H; xant(PiPr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphine)xanthene) coordinate the B–H bond of Boranes trans to the ligand X. As a consequence, elongated σ-Borane and σ-Borane pincer–POP–osmium complexes have been isolated and fully characterized. The interaction between the metal fragment and the coordinated B–H has been analyzed as a function of X, from spectroscopic, X-ray diffraction, and theoretical points of view. The dinuclear complex [(Os(H···H){κ3-P,O,P-[xant(PiPr2)2]})2(μ-Cl)2][BF4]2 (3) reacts with catecholBorane (HBcat) and pinacolBorane (HBpin) to give the elongated σ-Borane Derivative OsHCl(η2-H-BR2){κ3-P,O,P-[xant(PiPr2)2]} (BR2 = Bcat (4) and Bpin (5)), as well as H2, FBR2, and BF3. The elongated σ-Borane character of 4 and 5 is supported by X-ray diffraction analysis and DFT-optimized structures of both compounds, which show distances between the coordinated B and H atoms of the Borane in the range of 1.6–1.7 Å. AIM analysis of 4 reveals a triangular topology for the OsHB unit involving Os–B, Os–H, and B–H bond critical points and a ring critical point. In contrast to 3, the reaction of tetrahydride complex OsH4{κ3-P,O,P-[xant(PiPr2)2]} (6) with HBcat leads to σ-Borane Derivative OsH2(η2-H-Bcat){κ3-P,O,P-[xant(PiPr2)2]} (7), which shows a distance between the atoms of the coordinated B–H bond in the range of 1.4–1.5 Å. AIM analysis for the OsHB unit of 7 only displays Os–B and B–H bond critical points; therefore, it lacks a similar topology
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An Entry to Stable Mixed Phosphine–Osmium–NHC Polyhydrides
2016Co-Authors: María L. Buil, Miguel A. Esteruelas, Israel Fernández, Juan J. F. Cardo, Enrique OñateAbstract:An entry to mixed phosphine–osmium–NHC polyhydride complexes is described, starting from the five-coordinate hydrido–alkylidyne compounds [OsHCl(CPh)(IPr)(PR3)]OTf (IPr = 1,3-bis(2,6-disopropylphenyl)imidazolylidene; OTf = CF3SO3; PR3 = PiPr3 (1), PPh3 (2)). The experimental procedure involves the borylation of the Os–C triple bond of 1 and 2 with NaBH4 and the subsequent alcoholysis of the borylation products OsH2Cl(η2-H-BCH2Ph)(IPr)(PR3) (PR3 = PiPr3 (3), PPh3 (4)) or OsH2(η2:η2:H2BCH2Ph)(IPr)(PiPr3) (5). Stirring of 3 in 2-propanol affords the five coordinate chloride–trihydride OsH3Cl(IPr)(PiPr3)2 (6), which reacts with NaBH4 to give OsH3(κ2-H2BH2)(IPr)(PiPr3) (7). This trihydride–tetrahydrideborate Derivative and its PPh3 counterpart OsH3(κ2-H2BH2)(IPr)(PPh3) (8) can be also obtained in a one-pot procedure, starting from 1 and 2 and using methanol at −60 °C instead of 2-propanol as alcoholysis agent. The bonding situation in 7 and 8, analyzed by DFT calculations using AIM and NBO methods, resembles that found in B2H6 and contrasts with the bonding situation in the bis-σ-Borane Derivative 5. Stirring of 7 and 8 in 2-propanol leads to the corresponding d2-hexahydride Derivatives OsH6(IPr)(PR3) (PR3 = PiPr3 (9), PPh3 (10)), which reduce the CN triple bond of benzonitrile and promote the subsequent chelate-assisted ortho-CH bond activation of the resulting phenylmethanimine, to form the trihydride compounds OsH3{κ2-N,C-(NHCH-C6H4)}(IPr)(PR3)2 (PR3 = PiPr3 (11), PPh3 (12)), containing a stabilized orthometalated aldimine
Enrique Oñate - One of the best experts on this subject based on the ideXlab platform.
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Elongated σ-Borane versus σ-Borane in Pincer–POP–Osmium Complexes
Organometallics, 2017Co-Authors: Miguel A. Esteruelas, Israel Fernández, Cristina García-yebra, Jaime Martín, Enrique OñateAbstract:Square pyramidal metal fragments OsHX{κ3-P,O,P-[xant(PiPr2)2]} (X = Cl, H; xant(PiPr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphine)xanthene) coordinate the B–H bond of Boranes trans to the ligand X. As a consequence, elongated σ-Borane and σ-Borane pincer–POP–osmium complexes have been isolated and fully characterized. The interaction between the metal fragment and the coordinated B–H has been analyzed as a function of X, from spectroscopic, X-ray diffraction, and theoretical points of view. The dinuclear complex [(Os(H···H){κ3-P,O,P-[xant(PiPr2)2]})2(μ-Cl)2][BF4]2 (3) reacts with catecholBorane (HBcat) and pinacolBorane (HBpin) to give the elongated σ-Borane Derivative OsHCl(η2-H-BR2){κ3-P,O,P-[xant(PiPr2)2]} (BR2 = Bcat (4) and Bpin (5)), as well as H2, FBR2, and BF3. The elongated σ-Borane character of 4 and 5 is supported by X-ray diffraction analysis and DFT-optimized structures of both compounds, which show distances between the coordinated B and H atoms of the Borane in the range of 1.6–1.7 A. AIM...
Enrique Oñate - One of the best experts on this subject based on the ideXlab platform.
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Elongated σ‑Borane versus σ‑Borane in Pincer–POP–Osmium Complexes
2017Co-Authors: Miguel A. Esteruelas, Israel Fernández, Cristina García-yebra, Jaime Martín, Enrique OñateAbstract:Square pyramidal metal fragments OsHX{κ3-P,O,P-[xant(PiPr2)2]} (X = Cl, H; xant(PiPr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphine)xanthene) coordinate the B–H bond of Boranes trans to the ligand X. As a consequence, elongated σ-Borane and σ-Borane pincer–POP–osmium complexes have been isolated and fully characterized. The interaction between the metal fragment and the coordinated B–H has been analyzed as a function of X, from spectroscopic, X-ray diffraction, and theoretical points of view. The dinuclear complex [(Os(H···H){κ3-P,O,P-[xant(PiPr2)2]})2(μ-Cl)2][BF4]2 (3) reacts with catecholBorane (HBcat) and pinacolBorane (HBpin) to give the elongated σ-Borane Derivative OsHCl(η2-H-BR2){κ3-P,O,P-[xant(PiPr2)2]} (BR2 = Bcat (4) and Bpin (5)), as well as H2, FBR2, and BF3. The elongated σ-Borane character of 4 and 5 is supported by X-ray diffraction analysis and DFT-optimized structures of both compounds, which show distances between the coordinated B and H atoms of the Borane in the range of 1.6–1.7 Å. AIM analysis of 4 reveals a triangular topology for the OsHB unit involving Os–B, Os–H, and B–H bond critical points and a ring critical point. In contrast to 3, the reaction of tetrahydride complex OsH4{κ3-P,O,P-[xant(PiPr2)2]} (6) with HBcat leads to σ-Borane Derivative OsH2(η2-H-Bcat){κ3-P,O,P-[xant(PiPr2)2]} (7), which shows a distance between the atoms of the coordinated B–H bond in the range of 1.4–1.5 Å. AIM analysis for the OsHB unit of 7 only displays Os–B and B–H bond critical points; therefore, it lacks a similar topology
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An Entry to Stable Mixed Phosphine–Osmium–NHC Polyhydrides
2016Co-Authors: María L. Buil, Miguel A. Esteruelas, Israel Fernández, Juan J. F. Cardo, Enrique OñateAbstract:An entry to mixed phosphine–osmium–NHC polyhydride complexes is described, starting from the five-coordinate hydrido–alkylidyne compounds [OsHCl(CPh)(IPr)(PR3)]OTf (IPr = 1,3-bis(2,6-disopropylphenyl)imidazolylidene; OTf = CF3SO3; PR3 = PiPr3 (1), PPh3 (2)). The experimental procedure involves the borylation of the Os–C triple bond of 1 and 2 with NaBH4 and the subsequent alcoholysis of the borylation products OsH2Cl(η2-H-BCH2Ph)(IPr)(PR3) (PR3 = PiPr3 (3), PPh3 (4)) or OsH2(η2:η2:H2BCH2Ph)(IPr)(PiPr3) (5). Stirring of 3 in 2-propanol affords the five coordinate chloride–trihydride OsH3Cl(IPr)(PiPr3)2 (6), which reacts with NaBH4 to give OsH3(κ2-H2BH2)(IPr)(PiPr3) (7). This trihydride–tetrahydrideborate Derivative and its PPh3 counterpart OsH3(κ2-H2BH2)(IPr)(PPh3) (8) can be also obtained in a one-pot procedure, starting from 1 and 2 and using methanol at −60 °C instead of 2-propanol as alcoholysis agent. The bonding situation in 7 and 8, analyzed by DFT calculations using AIM and NBO methods, resembles that found in B2H6 and contrasts with the bonding situation in the bis-σ-Borane Derivative 5. Stirring of 7 and 8 in 2-propanol leads to the corresponding d2-hexahydride Derivatives OsH6(IPr)(PR3) (PR3 = PiPr3 (9), PPh3 (10)), which reduce the CN triple bond of benzonitrile and promote the subsequent chelate-assisted ortho-CH bond activation of the resulting phenylmethanimine, to form the trihydride compounds OsH3{κ2-N,C-(NHCH-C6H4)}(IPr)(PR3)2 (PR3 = PiPr3 (11), PPh3 (12)), containing a stabilized orthometalated aldimine
Oñate Enrique - One of the best experts on this subject based on the ideXlab platform.
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Elongated σ-Borane versus σ-Borane in pincer–POP–osmium complexes
'American Chemical Society (ACS)', 2017Co-Authors: Esteruelas, Miguel A., Fernández Israel, García-yebra Cristina, Martín Jaime, Oñate EnriqueAbstract:Square pyramidal metal fragments OsHX{κ3-P,O,P-[xant(PiPr2)2]} (X = Cl, H; xant(PiPr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphine)xanthene) coordinate the B–H bond of Boranes trans to the ligand X. As a consequence, elongated σ-Borane and σ-Borane pincer–POP–osmium complexes have been isolated and fully characterized. The interaction between the metal fragment and the coordinated B–H has been analyzed as a function of X, from spectroscopic, X-ray diffraction, and theoretical points of view. The dinuclear complex [(Os(H···H){κ3-P,O,P-[xant(PiPr2)2]})2(μ-Cl)2][BF4]2 (3) reacts with catecholBorane (HBcat) and pinacolBorane (HBpin) to give the elongated σ-Borane Derivative OsHCl(η2-H-BR2){κ3-P,O,P-[xant(PiPr2)2]} (BR2 = Bcat (4) and Bpin (5)), as well as H2, FBR2, and BF3. The elongated σ-Borane character of 4 and 5 is supported by X-ray diffraction analysis and DFT-optimized structures of both compounds, which show distances between the coordinated B and H atoms of the Borane in the range of 1.6–1.7 Å. AIM analysis of 4 reveals a triangular topology for the OsHB unit involving Os–B, Os–H, and B–H bond critical points and a ring critical point. In contrast to 3, the reaction of tetrahydride complex OsH4{κ3-P,O,P-[xant(PiPr2)2]} (6) with HBcat leads to σ-Borane Derivative OsH2(η2-H-Bcat){κ3-P,O,P-[xant(PiPr2)2]} (7), which shows a distance between the atoms of the coordinated B–H bond in the range of 1.4–1.5 Å. AIM analysis for the OsHB unit of 7 only displays Os–B and B–H bond critical points; therefore, it lacks a similar topology.Financial support from MINECO of Spain (Projects CTQ2013-44303-P, CTQ2014-52799-P, CTQ2016-78205-P and CTQ2016-81797-REDC), Diputación General de Aragón (E35), FEDER, and European Social Fund is acknowledged.Peer reviewe
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An entry to stable mixed phosphine–osmium–NHC polyhydrides
'American Chemical Society (ACS)', 2016Co-Authors: Buil, María L., Esteruelas, Miguel A., Fernández Israel, Cardo, Juan F., Oñate EnriqueAbstract:An entry to mixed phosphine–osmium–NHC polyhydride complexes is described, starting from the five-coordinate hydrido–alkylidyne compounds [OsHCl(≡CPh)(IPr)(PR3)]OTf (IPr = 1,3-bis(2,6-disopropylphenyl)imidazolylidene; OTf = CF3SO3; PR3 = PiPr3 (1), PPh3 (2)). The experimental procedure involves the borylation of the Os–C triple bond of 1 and 2 with NaBH4 and the subsequent alcoholysis of the borylation products OsH2Cl(η2-H-BCH2Ph)(IPr)(PR3) (PR3 = PiPr3 (3), PPh3 (4)) or OsH2(η2:η2:H2BCH2Ph)(IPr)(PiPr3) (5). Stirring of 3 in 2-propanol affords the five coordinate chloride–trihydride OsH3Cl(IPr)(PiPr3)2 (6), which reacts with NaBH4 to give OsH3(κ2-H2BH2)(IPr)(PiPr3) (7). This trihydride–tetrahydrideborate Derivative and its PPh3 counterpart OsH3(κ2-H2BH2)(IPr)(PPh3) (8) can be also obtained in a one-pot procedure, starting from 1 and 2 and using methanol at −60 °C instead of 2-propanol as alcoholysis agent. The bonding situation in 7 and 8, analyzed by DFT calculations using AIM and NBO methods, resembles that found in B2H6 and contrasts with the bonding situation in the bis-σ-Borane Derivative 5. Stirring of 7 and 8 in 2-propanol leads to the corresponding d2-hexahydride Derivatives OsH6(IPr)(PR3) (PR3 = PiPr3 (9), PPh3 (10)), which reduce the C≡N triple bond of benzonitrile and promote the subsequent chelate-assisted ortho-CH bond activation of the resulting phenylmethanimine, to form the trihydride compounds OsH3{κ2-N,C-(NH═CH-C6H4)}(IPr)(PR3)2 (PR3 = PiPr3 (11), PPh3 (12)), containing a stabilized orthometalated aldimine.Financial support from the Spanish MINECO (Projects CTQ2014-52799-P, CTQ2013-44303-P, Red de Excelencia Consolider CTQ2014-51912-REDC), the DGA (E35) and the European Social Fund (FSE) and FEDER is acknowledged. J. J. F. acknowledges support via a pre-doctoral fellowship from the DGA.Peer reviewe
Cristina García-yebra - One of the best experts on this subject based on the ideXlab platform.
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Elongated σ-Borane versus σ-Borane in Pincer–POP–Osmium Complexes
Organometallics, 2017Co-Authors: Miguel A. Esteruelas, Israel Fernández, Cristina García-yebra, Jaime Martín, Enrique OñateAbstract:Square pyramidal metal fragments OsHX{κ3-P,O,P-[xant(PiPr2)2]} (X = Cl, H; xant(PiPr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphine)xanthene) coordinate the B–H bond of Boranes trans to the ligand X. As a consequence, elongated σ-Borane and σ-Borane pincer–POP–osmium complexes have been isolated and fully characterized. The interaction between the metal fragment and the coordinated B–H has been analyzed as a function of X, from spectroscopic, X-ray diffraction, and theoretical points of view. The dinuclear complex [(Os(H···H){κ3-P,O,P-[xant(PiPr2)2]})2(μ-Cl)2][BF4]2 (3) reacts with catecholBorane (HBcat) and pinacolBorane (HBpin) to give the elongated σ-Borane Derivative OsHCl(η2-H-BR2){κ3-P,O,P-[xant(PiPr2)2]} (BR2 = Bcat (4) and Bpin (5)), as well as H2, FBR2, and BF3. The elongated σ-Borane character of 4 and 5 is supported by X-ray diffraction analysis and DFT-optimized structures of both compounds, which show distances between the coordinated B and H atoms of the Borane in the range of 1.6–1.7 A. AIM...