Four homo-and heteroannularly bridged ferrocenyl diphosphine ligands have been tested in enantios... more Four homo-and heteroannularly bridged ferrocenyl diphosphine ligands have been tested in enantioselective hydrogenations of olefins, ketones, and imines. The influence of the ligand backbone on the enantioselectivity has been studied.
The ligands 4,6-bis(pyrazol-1-yl)pyrimidine (bpzpm) and 4,6-bis(4-methylpyrazol-1-yl)pyrimidine (... more The ligands 4,6-bis(pyrazol-1-yl)pyrimidine (bpzpm) and 4,6-bis(4-methylpyrazol-1-yl)pyrimidine (Me-bpzpm) were synthesized and their reactions with some palladium derivatives explored. Mononuclear or dinuclear neutral or cationic complexes were obtained by reaction of the ligands with 1 or 2 equiv of Pd(C6XF4)2(cod) (cod = 1,5-cyclooctadiene; X = F, H) or the palladium fragment [Pd(eta 3-2-Me-C3H4)(S)2]+ (S = acetone). The reaction of the dinuclear derivatives with 1 equiv of the respective free ligand immediately led to the regeneration of the mononuclear complexes. Except in the case of the synthesis of [[Pd(C6HF4)2][Pd(C6F5)2](bpzpm)], where two similar metallic groups are present, all attempts to obtain dinuclear asymmetric complexes with two different palladium fragments failed. Instead, the dinuclear symmetric complexes were formed. This result could be considered as an example of molecular recognition with the ligand acting as a ditopic receptor. This behavior is comparable to chemical symbiosis but in this case applied to the ligand rather than to the metal center as occurs normally. The polyfluorophenyl rings are situated on average in a perpendicular orientation with respect to the coordination plane. Their restricted rotation results in several atropoisomers for the complexes with m-C6HF4. Different cross-reaction experiments were carried out, and these showed the mobility of the metallic fragments, with the more difficult process being that involving the more strongly bonded polyfluorophenyl palladium groups. By means of 1H NMR variable temperature studies, the interconversion of the two isomers of [[Pd(eta 3-C4H7)]2-(bpzpm)]Tf2 (Tf = CF3SO3) was analyzed. In the case of [[Pd(eta 3-C4H7)](bpzpm)]Tf the existence of two processes, an intramolecular apparent allyl rotation and an intermolecular exchange of the allylpalladium fragments, has been demonstrated. Different delta Gc++ values at the coalescence temperatures have also been determined. An X-ray single-crystal analysis was carried out on [[Pd(eta 3-C4H7)]2(bpzpm)]Tf2, which crystallizes in the monoclinic system, space group I2/m, with a = 9.368(2), b = 16.191(3), c = 20.228(6) A, beta = 101.26(3), and Z = 4. Compound [[Pd(C6HF4)2](bpzpm)] crystallized in the triclinic system, space group P1, with a = 8.845(6), b = 12.6609(9), c = 12.826(3) A, alpha = 88.45(2), beta = 74.36(3), gamma = 89.32(2), and Z = 2.
Journal of The Chemical Society-dalton Transactions, 2001
J. Chem. Soc., Dalton Trans., 2001, 2417-2424 DOI:10.1039/B101912K (Paper). NMR study on the coor... more J. Chem. Soc., Dalton Trans., 2001, 2417-2424 DOI:10.1039/B101912K (Paper). NMR study on the coordination of dibenzylideneacetone to chiral palladium(0) units. Fluxional behaviour including an intramolecular double bond exchange. ...
... Michel Etienne,* Bruno Donnadieu, René Mathieu, Juan Fernández Baeza, Felix Jalón, ... more ... Michel Etienne,* Bruno Donnadieu, René Mathieu, Juan Fernández Baeza, Felix Jalón, Antonio Otero, and Maria Esther Rodrigo-Blanco . Laboratoire de Chimie de Coordination du CNRS, UPR 8241, 205 Route ...
... A. Jalón, Blanca R. Manzano,* and Jerónimo Rodríguez-de la Fuente. Departamento de Química ... more ... A. Jalón, Blanca R. Manzano,* and Jerónimo Rodríguez-de la Fuente. Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Campus Universitario, 13071 Ciudad Real, Spain. Miranda Vrahami, Brigitte Jedlicka, and Walter Weissensteiner* . ...
New cationic 2-Me-allylpalladium complexes were prepared with the N, N-donor chelate ligands bis ... more New cationic 2-Me-allylpalladium complexes were prepared with the N, N-donor chelate ligands bis (pyrazol-1-yl)(R) methane (R= anisol-2-yl, bpzmArOMe; 2-hydroxyphenyl, bpzmArOH) and bis (3, 5-dimethylpyrazol-1-yl)(R) methane (R= anisol-2-yl, bpz* mArOMe; ...
... Blanca R. Manzano,* Félix A. Jalón, Felipe Gómez-de la Torre, Ana M. López-Agenjo, ... more ... Blanca R. Manzano,* Félix A. Jalón, Felipe Gómez-de la Torre, Ana M. López-Agenjo, Ana M. Rodríguez, § Kurt Mereiter, Walter Weissensteiner,* and Thomas Sturm. Facultad de Químicas, Universidad de Castilla-La Mancha, Avda. ...
... Jedlicka a , Richard E. Rülke a , 1 , Walter Weissensteiner a , Corresponding Author Contact ... more ... Jedlicka a , Richard E. Rülke a , 1 , Walter Weissensteiner a , Corresponding Author Contact Information , Rafael Fernández-Galán b , Félix A. Jalón b , Blanca R. Manzano b , Corresponding Author Contact Information , Jerónimo Rodríguez-de la ... [25] KJ Cavell, DJ Stufkens and ...
... Agustín Caballero a , M. Carmen Carrión a , Gustavo Espino b , Félix A. Jalón Corresponding A... more ... Agustín Caballero a , M. Carmen Carrión a , Gustavo Espino b , Félix A. Jalón Corresponding Author Contact Information , E-mail The Corresponding Author , a and Blanca R. Manzano a. a Departemento de Química Inorgnica, Org. ...
Meijer et al. studied the preparation of supramolecular complexes of melamine with the imides suc... more Meijer et al. studied the preparation of supramolecular complexes of melamine with the imides succinimide, glutarimide and 1-N-propylthymine.(13) On using succinimide, a complex with a 1:1 melamine:succinimide ratio was obtained and this was extended in a laminar ...
New examples of the fluxional behavior of (η3-allyl)palla-dium complexes are described. Variable-... more New examples of the fluxional behavior of (η3-allyl)palla-dium complexes are described. Variable-temperature experiments and line-shape analysis of two (η3-allyl)palladium complexes containing 2-(1H-pyrazol-1-yl)azine ligands were performed in order to determine the activation free energies, enthalpies and entropies of the process. A dissociative mechanism pointing to a selective Pd-N cleavage is proposed on the basis of these results and NOE experiments above and below the coalescence temperature.
Four homo-and heteroannularly bridged ferrocenyl diphosphine ligands have been tested in enantios... more Four homo-and heteroannularly bridged ferrocenyl diphosphine ligands have been tested in enantioselective hydrogenations of olefins, ketones, and imines. The influence of the ligand backbone on the enantioselectivity has been studied.
The ligands 4,6-bis(pyrazol-1-yl)pyrimidine (bpzpm) and 4,6-bis(4-methylpyrazol-1-yl)pyrimidine (... more The ligands 4,6-bis(pyrazol-1-yl)pyrimidine (bpzpm) and 4,6-bis(4-methylpyrazol-1-yl)pyrimidine (Me-bpzpm) were synthesized and their reactions with some palladium derivatives explored. Mononuclear or dinuclear neutral or cationic complexes were obtained by reaction of the ligands with 1 or 2 equiv of Pd(C6XF4)2(cod) (cod = 1,5-cyclooctadiene; X = F, H) or the palladium fragment [Pd(eta 3-2-Me-C3H4)(S)2]+ (S = acetone). The reaction of the dinuclear derivatives with 1 equiv of the respective free ligand immediately led to the regeneration of the mononuclear complexes. Except in the case of the synthesis of [[Pd(C6HF4)2][Pd(C6F5)2](bpzpm)], where two similar metallic groups are present, all attempts to obtain dinuclear asymmetric complexes with two different palladium fragments failed. Instead, the dinuclear symmetric complexes were formed. This result could be considered as an example of molecular recognition with the ligand acting as a ditopic receptor. This behavior is comparable to chemical symbiosis but in this case applied to the ligand rather than to the metal center as occurs normally. The polyfluorophenyl rings are situated on average in a perpendicular orientation with respect to the coordination plane. Their restricted rotation results in several atropoisomers for the complexes with m-C6HF4. Different cross-reaction experiments were carried out, and these showed the mobility of the metallic fragments, with the more difficult process being that involving the more strongly bonded polyfluorophenyl palladium groups. By means of 1H NMR variable temperature studies, the interconversion of the two isomers of [[Pd(eta 3-C4H7)]2-(bpzpm)]Tf2 (Tf = CF3SO3) was analyzed. In the case of [[Pd(eta 3-C4H7)](bpzpm)]Tf the existence of two processes, an intramolecular apparent allyl rotation and an intermolecular exchange of the allylpalladium fragments, has been demonstrated. Different delta Gc++ values at the coalescence temperatures have also been determined. An X-ray single-crystal analysis was carried out on [[Pd(eta 3-C4H7)]2(bpzpm)]Tf2, which crystallizes in the monoclinic system, space group I2/m, with a = 9.368(2), b = 16.191(3), c = 20.228(6) A, beta = 101.26(3), and Z = 4. Compound [[Pd(C6HF4)2](bpzpm)] crystallized in the triclinic system, space group P1, with a = 8.845(6), b = 12.6609(9), c = 12.826(3) A, alpha = 88.45(2), beta = 74.36(3), gamma = 89.32(2), and Z = 2.
Journal of The Chemical Society-dalton Transactions, 2001
J. Chem. Soc., Dalton Trans., 2001, 2417-2424 DOI:10.1039/B101912K (Paper). NMR study on the coor... more J. Chem. Soc., Dalton Trans., 2001, 2417-2424 DOI:10.1039/B101912K (Paper). NMR study on the coordination of dibenzylideneacetone to chiral palladium(0) units. Fluxional behaviour including an intramolecular double bond exchange. ...
... Michel Etienne,* Bruno Donnadieu, René Mathieu, Juan Fernández Baeza, Felix Jalón, ... more ... Michel Etienne,* Bruno Donnadieu, René Mathieu, Juan Fernández Baeza, Felix Jalón, Antonio Otero, and Maria Esther Rodrigo-Blanco . Laboratoire de Chimie de Coordination du CNRS, UPR 8241, 205 Route ...
... A. Jalón, Blanca R. Manzano,* and Jerónimo Rodríguez-de la Fuente. Departamento de Química ... more ... A. Jalón, Blanca R. Manzano,* and Jerónimo Rodríguez-de la Fuente. Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Campus Universitario, 13071 Ciudad Real, Spain. Miranda Vrahami, Brigitte Jedlicka, and Walter Weissensteiner* . ...
New cationic 2-Me-allylpalladium complexes were prepared with the N, N-donor chelate ligands bis ... more New cationic 2-Me-allylpalladium complexes were prepared with the N, N-donor chelate ligands bis (pyrazol-1-yl)(R) methane (R= anisol-2-yl, bpzmArOMe; 2-hydroxyphenyl, bpzmArOH) and bis (3, 5-dimethylpyrazol-1-yl)(R) methane (R= anisol-2-yl, bpz* mArOMe; ...
... Blanca R. Manzano,* Félix A. Jalón, Felipe Gómez-de la Torre, Ana M. López-Agenjo, ... more ... Blanca R. Manzano,* Félix A. Jalón, Felipe Gómez-de la Torre, Ana M. López-Agenjo, Ana M. Rodríguez, § Kurt Mereiter, Walter Weissensteiner,* and Thomas Sturm. Facultad de Químicas, Universidad de Castilla-La Mancha, Avda. ...
... Jedlicka a , Richard E. Rülke a , 1 , Walter Weissensteiner a , Corresponding Author Contact ... more ... Jedlicka a , Richard E. Rülke a , 1 , Walter Weissensteiner a , Corresponding Author Contact Information , Rafael Fernández-Galán b , Félix A. Jalón b , Blanca R. Manzano b , Corresponding Author Contact Information , Jerónimo Rodríguez-de la ... [25] KJ Cavell, DJ Stufkens and ...
... Agustín Caballero a , M. Carmen Carrión a , Gustavo Espino b , Félix A. Jalón Corresponding A... more ... Agustín Caballero a , M. Carmen Carrión a , Gustavo Espino b , Félix A. Jalón Corresponding Author Contact Information , E-mail The Corresponding Author , a and Blanca R. Manzano a. a Departemento de Química Inorgnica, Org. ...
Meijer et al. studied the preparation of supramolecular complexes of melamine with the imides suc... more Meijer et al. studied the preparation of supramolecular complexes of melamine with the imides succinimide, glutarimide and 1-N-propylthymine.(13) On using succinimide, a complex with a 1:1 melamine:succinimide ratio was obtained and this was extended in a laminar ...
New examples of the fluxional behavior of (η3-allyl)palla-dium complexes are described. Variable-... more New examples of the fluxional behavior of (η3-allyl)palla-dium complexes are described. Variable-temperature experiments and line-shape analysis of two (η3-allyl)palladium complexes containing 2-(1H-pyrazol-1-yl)azine ligands were performed in order to determine the activation free energies, enthalpies and entropies of the process. A dissociative mechanism pointing to a selective Pd-N cleavage is proposed on the basis of these results and NOE experiments above and below the coalescence temperature.
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Papers by FELIX A. JALON