daniel padron - Academia.edu (original) (raw)
Papers by daniel padron
Offshore Technology Conference, 1985
Zeitschrift für anorganische und allgemeine Chemie, 2013
ABSTRACT Syntheses for 2-[1-(diarylphosphinoyl)-1-(pyridin-2-yl)methyl]pyridines, (8a, b), and 2-... more ABSTRACT Syntheses for 2-[1-(diarylphosphinoyl)-1-(pyridin-2-yl)methyl]pyridines, (8a, b), and 2-[1-(diarylphosphinoyl)-1, 1-bis(methylpyridin-2yl)methyl]pyridines, (11a, b), (Ar = C6H5 and 2-CF3C6H4), based on substitution of 2-methylpyridine fragments onto the exo methylene carbon atom of 2-[(diaryl)phosphinoylmethyl]pyridine platforms, are described. N-oxidations of 8a, b and 11a, b produced the 2-[1-(diarylphosphinoyl)-1-(1-oxy-pyridin-2yl)methyl]pyridine N-oxides (5a, b) and the 2-[1-(diarylphosphinoyl)-1, 1-bis(1-oxy-methylpyridin-2-yl)methyl]pyridines (6a, b), respectively. The “short-arm“ pyridine fragment of 11a, b resists N-oxidation, and the fully oxidized molecules, 2-[1-(diarylphosphinoyl)-1, 1-bis(1-oxy-methylpyridin-2-yl)methyl]pyridine N-oxides (7a, b) were not isolated. Molecular mechanics calculations for gas phase 1:1 ligand/lanthanide complexes indicated that 5a should accommodate a tridentate NO(meNO)PO coordination mode with minimal steric strain. In contrast, 7a cannot form tetradentate NO(meNO)2PO chelates; however, tridentate binding should be accessible with minimal ligand strain. Coordination complexes of 8a, b, 5a, b, 6a, b and 11a, b with Ln(NO3)3 salts were isolated and a X-ray crystal structure for [Er(8a)(NO3)3(MeOH)2]·CH2Cl2, revealed a monodentate Er–O=P interaction. On the other hand, complexes formed by a more symmetrical trifunctional phenylphosphino-bis-2-methylpyridine N, N, P-trioxide ligand, (meNO)2PO*, {La[(meNO)2PO*)](OTf)2(MeOH)3(H2O)+}(OTf–) and {Pr[(meNO)2PO*)](OTf)(MeOH)4+}(OTf–)2, realized a tridentate coordination mode. Solvent extraction behaviors for EuIII and AmIII in nitric acid solutions using 5a, b, 6a, b, Ph3PO and the parent bifunctional ligand 2-[(diphenylphosphanyl)methyl]pyridine N, P-dioxide (3a) in 1, 2-dichloroethane were assessed, and 5a, b and 6a, b were found to behave more like Ph3PO than 3a.
Inorganica Chimica Acta, 2013
Several new coordination complexes of Co 2+ , Ni 2+ , Cu 2+ and Zn 2+ were synthesized by the rea... more Several new coordination complexes of Co 2+ , Ni 2+ , Cu 2+ and Zn 2+ were synthesized by the reaction of their corresponding tetrafluoroborate salts with 2-(diphenylphosphinomethyl)pyridine N,P dioxide, L. All structures were determined by single-crystal X-ray crystallography showing an octahedral environment around the metal centers. Single crystals of M(BF 4 ) 2 L 2 (S) 2 (M = Co 2+ , Ni 2+ or Zn 2+ ; S = MeOH or CH 3 CN) were obtained at À5°C by slow diffusion of ether into solutions of these complexes. When these crystals were re-dissolved in methanol and allowed to grow again at room temperature using the same technique and solvent system, the product obtained presented a 3:1 ratio ligand-to-metal. The complex [Cu(BF 4 ) 2-L 2 (MeOH)](BF 4 ), exhibits two units of L, one molecule of MeOH and one counter-anion coordinated to the Cu 2+ center. This can be attributed to the steric restrictions generated by the lower symmetry in this complex, a product of significant Jahn-Teller effects, which favors a long range interaction between the metal center and a less coordinative counter-anion, compared to a MeOH unit. A 1:1 ligand-to-metal ratio complex of Ni 2+ was also obtained by allowing the starting materials to react for only a short time. Attempts to obtain single crystal of complexes of Co 2+ , Cu 2+ or Zn 2+ in a 1:1 ratio were not successful. The resulting 3:1 ligand-to-metal products were fully characterized by elemental analysis, UV-Vis spectroscopy and FT-IR spectroscopy.
European Journal of Inorganic Chemistry, 2013
The coordination properties of the 2-[(diphenylphosphanyl)methyl]pyridine N,P-dioxide ligand towa... more The coordination properties of the 2-[(diphenylphosphanyl)methyl]pyridine N,P-dioxide ligand towards three different silver(I) salts are described. The molecular structures of the coordination complexes obtained showed a strong dependence on the 2-[(diphenylphosphanyl)methyl]pyridine N,Pdioxide ligand and the binding ability of the counterion. The strongly binding trifluoroacetate ion yielded a unique planar
Offshore Technology Conference, 1985
Zeitschrift für anorganische und allgemeine Chemie, 2013
ABSTRACT Syntheses for 2-[1-(diarylphosphinoyl)-1-(pyridin-2-yl)methyl]pyridines, (8a, b), and 2-... more ABSTRACT Syntheses for 2-[1-(diarylphosphinoyl)-1-(pyridin-2-yl)methyl]pyridines, (8a, b), and 2-[1-(diarylphosphinoyl)-1, 1-bis(methylpyridin-2yl)methyl]pyridines, (11a, b), (Ar = C6H5 and 2-CF3C6H4), based on substitution of 2-methylpyridine fragments onto the exo methylene carbon atom of 2-[(diaryl)phosphinoylmethyl]pyridine platforms, are described. N-oxidations of 8a, b and 11a, b produced the 2-[1-(diarylphosphinoyl)-1-(1-oxy-pyridin-2yl)methyl]pyridine N-oxides (5a, b) and the 2-[1-(diarylphosphinoyl)-1, 1-bis(1-oxy-methylpyridin-2-yl)methyl]pyridines (6a, b), respectively. The “short-arm“ pyridine fragment of 11a, b resists N-oxidation, and the fully oxidized molecules, 2-[1-(diarylphosphinoyl)-1, 1-bis(1-oxy-methylpyridin-2-yl)methyl]pyridine N-oxides (7a, b) were not isolated. Molecular mechanics calculations for gas phase 1:1 ligand/lanthanide complexes indicated that 5a should accommodate a tridentate NO(meNO)PO coordination mode with minimal steric strain. In contrast, 7a cannot form tetradentate NO(meNO)2PO chelates; however, tridentate binding should be accessible with minimal ligand strain. Coordination complexes of 8a, b, 5a, b, 6a, b and 11a, b with Ln(NO3)3 salts were isolated and a X-ray crystal structure for [Er(8a)(NO3)3(MeOH)2]·CH2Cl2, revealed a monodentate Er–O=P interaction. On the other hand, complexes formed by a more symmetrical trifunctional phenylphosphino-bis-2-methylpyridine N, N, P-trioxide ligand, (meNO)2PO*, {La[(meNO)2PO*)](OTf)2(MeOH)3(H2O)+}(OTf–) and {Pr[(meNO)2PO*)](OTf)(MeOH)4+}(OTf–)2, realized a tridentate coordination mode. Solvent extraction behaviors for EuIII and AmIII in nitric acid solutions using 5a, b, 6a, b, Ph3PO and the parent bifunctional ligand 2-[(diphenylphosphanyl)methyl]pyridine N, P-dioxide (3a) in 1, 2-dichloroethane were assessed, and 5a, b and 6a, b were found to behave more like Ph3PO than 3a.
Inorganica Chimica Acta, 2013
Several new coordination complexes of Co 2+ , Ni 2+ , Cu 2+ and Zn 2+ were synthesized by the rea... more Several new coordination complexes of Co 2+ , Ni 2+ , Cu 2+ and Zn 2+ were synthesized by the reaction of their corresponding tetrafluoroborate salts with 2-(diphenylphosphinomethyl)pyridine N,P dioxide, L. All structures were determined by single-crystal X-ray crystallography showing an octahedral environment around the metal centers. Single crystals of M(BF 4 ) 2 L 2 (S) 2 (M = Co 2+ , Ni 2+ or Zn 2+ ; S = MeOH or CH 3 CN) were obtained at À5°C by slow diffusion of ether into solutions of these complexes. When these crystals were re-dissolved in methanol and allowed to grow again at room temperature using the same technique and solvent system, the product obtained presented a 3:1 ratio ligand-to-metal. The complex [Cu(BF 4 ) 2-L 2 (MeOH)](BF 4 ), exhibits two units of L, one molecule of MeOH and one counter-anion coordinated to the Cu 2+ center. This can be attributed to the steric restrictions generated by the lower symmetry in this complex, a product of significant Jahn-Teller effects, which favors a long range interaction between the metal center and a less coordinative counter-anion, compared to a MeOH unit. A 1:1 ligand-to-metal ratio complex of Ni 2+ was also obtained by allowing the starting materials to react for only a short time. Attempts to obtain single crystal of complexes of Co 2+ , Cu 2+ or Zn 2+ in a 1:1 ratio were not successful. The resulting 3:1 ligand-to-metal products were fully characterized by elemental analysis, UV-Vis spectroscopy and FT-IR spectroscopy.
European Journal of Inorganic Chemistry, 2013
The coordination properties of the 2-[(diphenylphosphanyl)methyl]pyridine N,P-dioxide ligand towa... more The coordination properties of the 2-[(diphenylphosphanyl)methyl]pyridine N,P-dioxide ligand towards three different silver(I) salts are described. The molecular structures of the coordination complexes obtained showed a strong dependence on the 2-[(diphenylphosphanyl)methyl]pyridine N,Pdioxide ligand and the binding ability of the counterion. The strongly binding trifluoroacetate ion yielded a unique planar