Gilles Alcaraz - Academia.edu (original) (raw)
Papers by Gilles Alcaraz
Chemistry (Weinheim an der Bergstrasse, Germany), Jan 7, 2015
We recently disclosed a new ruthenium-catalyzed dehydrogenative cyclization process (CDC) of diam... more We recently disclosed a new ruthenium-catalyzed dehydrogenative cyclization process (CDC) of diamine-monoboranes leading to cyclic diaminoboranes. In the present study, the CDC reaction has been successfully extended to a larger number of diamine-monoboranes (4-7) and to one amine-borane alcohol precursor (8). The corresponding NB(H)N- and NB(H)O-containing cyclic diaminoboranes (12-15) and oxazaborolidine (16) were obtained in good to high yields. Multiple substitution patterns on the starting amine-borane substrates were evaluated and the reaction was also performed with chiral substrates. Efforts have been spent to understand the mechanism of the ruthenium CDC process. In addition to a computational approach, a strategy enabling the kinetic discrimination on successive events of the catalytic process leading to the formation of the NB(H)N linkage was performed on the six-carbon chain diamine-monoborane 21 and completed with a (15) N NMR study. The long-life bis-σ-borane ruthenium...
Coordination Chemistry Reviews, 2008
NMR has played a major role in the characterization of dihydrogen complexes and a number of polyh... more NMR has played a major role in the characterization of dihydrogen complexes and a number of polyhydrides have been reformulated as dihydrogen complexes on the basis of NMR data. If dihydrogen complexes remain the most widely studied class of σ-complexes, silane compounds are also well recognized as an important family of σ-complexes and more recently a few σ-borane compounds have
Journal of the American Chemical Society, Jan 18, 2007
Journal of the Chemical Society, Chemical Communications, 1993
... Adducts Gilles Alcaraz, Robert Reed, Antoine Baceiredo and Guy Bertrand" Laboratoire... more ... Adducts Gilles Alcaraz, Robert Reed, Antoine Baceiredo and Guy Bertrand" Laboratoire de Chimie de Coordination du CNRS, 205, route de Narbonne, 31077 Toulouse Cedex, France ... go%).? Downloaded by google on 24 April 2011 ...
Organometallics, 2010
ABSTRACT The coordination chemistry of diisopropylaminoborane H2B−NiPr2 with valence isoelectroni... more ABSTRACT The coordination chemistry of diisopropylaminoborane H2B−NiPr2 with valence isoelectronic metal fragments to form, essentially isostructural, [MH2(η2:η2-H2B−NiPr2)(PCy3)2]n+ (M = Ru, n = 0; Rh and Ir, n = 1) has been explored by a combination of X-ray crystallography, NMR spectroscopy, and computational techniques. In the solid state and solution the aminoborane interacts with the metal centers through one four-center four-electron interaction, forming bis(σ-B−H) complexes. The structural data point to tighter interactions between both the Ru and Ir congeners compared to the Rh with significantly shorter M···B distances in the first two. These tighter interactions are mirrored in the spectroscopic data, with the Ru and Ir complexes showing more deshielded 11B chemical shifts and 1H M−H−B resonances that are more shielded than observed for the rhodium complex. Analysis of the bonding between metal and borane using the NBO approach is in very good agreement with the variations in the geometrical and spectroscopic parameters. There is overall a stronger interaction between the borane and the metal fragment for neutral Ru compared to cationic Rh, with cationic Ir in an intermediate situation.
Organic Letters, 2006
A series of new dispiro[fluorene-9′,6,9′′,12-indeno[1,2b]fluorenes] (DSFIFs) that combine indenof... more A series of new dispiro[fluorene-9′,6,9′′,12-indeno[1,2b]fluorenes] (DSFIFs) that combine indenofluorene (IF) and spirobifluorene (SBF) architectural specificities have been prepared. Their anodic oxidations lead to the formation of nonsoluble transparent polymers. The photophysical and electrochemical properties of these new molecules have been evaluated for further blue OLED applications.
Journal of the American Chemical Society, 2008
Starting from RuHCl(H2)(PCy3)2, a terminal ruthenium mesitylborylene complex was obtained via dou... more Starting from RuHCl(H2)(PCy3)2, a terminal ruthenium mesitylborylene complex was obtained via double B-H bond activation of mesitylborane and concomitant release of dihydrogen, such a process being remarkably reversible.
Journal of the American Chemical Society, 2007
... Gilles Alcaraz,* Eric Clot,* Ulrike Helmstedt, Laure Vendier, and Sylviane Sabo-Etien... more ... Gilles Alcaraz,* Eric Clot,* Ulrike Helmstedt, Laure Vendier, and Sylviane Sabo-Etienne* . ... 13) Crestani, MG; Muñoz-Hernández, M.; Arévalo, A.; Acosta-Ramírez, A.; García, JJ J. Am. Chem. Soc.2005, 127, 18066−18073. ...
Journal of Organometallic Chemistry, 2009
The reaction of tert-butylborane with the bis(dihydrogen) complex RuH2(η2-H2)2(PCy3)2 leads to th... more The reaction of tert-butylborane with the bis(dihydrogen) complex RuH2(η2-H2)2(PCy3)2 leads to the corresponding bis σ-borane complex which is the first example of a monoalkylborane ruthenium bis σ-complex. An alternative route involves the reaction of RuHCl(η2-H2)(PCy3)2 with lithium tert-butylborohydride.
Journal of Organometallic Chemistry, 2005
Stereospecific Palladium-Catalyzed Borylation Reaction of 1-Alkenyl Halides with Diispropylaminob... more Stereospecific Palladium-Catalyzed Borylation Reaction of 1-Alkenyl Halides with Diispropylaminoborane. -(EUZENAT, L.; HORHANT, D.; BRIELLES, C.; ALCARAZ*, G.; VAULTIER, M.; J.
Journal of Materials Chemistry, 2008
Inorganic Chemistry, 1996
The structure of P,P-bis(diisopropylamino)-4-phenyl-1,3,2lambda(5)-diazaphosphete, 1a, has been d... more The structure of P,P-bis(diisopropylamino)-4-phenyl-1,3,2lambda(5)-diazaphosphete, 1a, has been determined by a single-crystal X-ray diffraction study (C(19)H(33)N(4)P, monoclinic system, space group P2(1), a = 9.482(1) Å, b = 11.374(3) Å, c = 9.668(2) Å, beta = 97.16(1) degrees, Z = 2). According to quantum chemical calculations at an RHF level of optimization utilizing the 6-31g(d,p) basis set, 1a has a zwitterionic structure with the negative charge delocalized on the NCN allylic fragment and the positive charge localized at the phosphorus. Heterocycle 1a reacts with water and benzaldehyde affording N-phosphoranylbenzamidine 3 (95% yield) and the expected aza-Wittig adduct 4 (85% yield), respectively. Addition of 1 equiv of methyl trifluoromethanesulfonate and of 2 equiv of BH(3).THF to 1a affords cyclic phosphonium salt 5 (94% yield) and the bis(borane) adduct 6a (90% yield), respectively. Dimethyl acetylenedicarboxylate slowly reacts with 1a giving rise to 1,3,4lambda(5)-diazaphosphinine, 9, in 70% yield. The X-ray crystal structures of products 2,3, and 6a are reported (2: C(26)H(38)N(5)P, monoclinic system, space group C2/c, a = 16.337(8) Å, b = 19.810(2) Å, c = 8.800(2) Å, beta = 117.68(2) degrees, Z = 4. 3: C(19)H(35)N(4)OP, orthorhombic system, space group P2(1)2(1)2(1), a = 9.090(1) Å, b = 12.955(2) Å, c = 17.860(3) Å, Z = 4. 6a: C(19)H(39)B(2)N(4)P, orthorhombic system, space group P2(1)2(1)2(1), a = 10.340(1) Å, b = 13.247(1) Å, c = 16.996(1) Å, Z = 4).
Dalton Transactions, 2013
The reactivity of the amino(cyano)borane (i)Pr(2)NBH(CN) (2) towards [RuH(2)(η(2)-H(2))(2)(PCy(3)... more The reactivity of the amino(cyano)borane (i)Pr(2)NBH(CN) (2) towards [RuH(2)(η(2)-H(2))(2)(PCy(3))(2)] (3) was investigated. Our study reveals that the formation of the bis(isocyanoborane) ruthenium complex [RuH(CN)(CN-BHN(i)Pr(2))(2)(PCy(3))(2)] (6) occurs via the intermediacy of the bis(σ-B-H) ruthenium complex [RuH(CN)(H(2)BN(i)Pr(2))(PCy(3))(2)] (5). This transformation involves BCN linkage isomerisation in 2. The diisopropylaminoborane ligand in 5 can be displaced to ultimately produce the bis(σ-borane) complex [RuH(2)(η(2):η(2)-H(2)BN(i)Pr(2))(PCy(3))(2)] (4) as a by-product.
Chemistry - A European Journal, 2007
Chemical Communications, 2009
The stoichiometric reaction of [Rh(COD)Cl](2) with the anion resulting from the deprotonation of ... more The stoichiometric reaction of [Rh(COD)Cl](2) with the anion resulting from the deprotonation of dppm(BH(3))(2) yielded a new alkyl Rh(I) complex; the coordination modes of the BH(3) groups are discussed on the basis of X-ray data, variable temperature multinuclear NMR experiments and DFT studies.
Chemical Communications, 2003
A series of octupolar molecules derived from the boroxine framework were designed and their optic... more A series of octupolar molecules derived from the boroxine framework were designed and their optical nonlinearities were investigated by performing harmonic light scattering experiments in solution; the molecules were found to combine excellent transparency in the near UV-visible region (lambdamax < or = 280 nm) and significant first-order hyperpolarisabilities (up to beta(0) = 56 x 10(-30) esu).
Chemical Communications, 2010
A novel cascade of reactions is designed to control in situ the deposition of noble metal islands... more A novel cascade of reactions is designed to control in situ the deposition of noble metal islands (e.g. Rh) on top of nanoparticles of a 3d metal (e.g. Fe, Co).
Chemical Communications, 2003
Thermal decomposition of hindered amine-borane adducts leads in high yields to monomeric (dialkyl... more Thermal decomposition of hindered amine-borane adducts leads in high yields to monomeric (dialkylamino)boranes R1R2N-BH2 (R1 and R2 = alkyl) that are new and efficient boron-sources in the Pd0 catalyzed borylation reaction affording monomeric aryl(dialkylamino)boranes R1R2N-BHR3 (R3 = aryl).
Chemistry (Weinheim an der Bergstrasse, Germany), Jan 7, 2015
We recently disclosed a new ruthenium-catalyzed dehydrogenative cyclization process (CDC) of diam... more We recently disclosed a new ruthenium-catalyzed dehydrogenative cyclization process (CDC) of diamine-monoboranes leading to cyclic diaminoboranes. In the present study, the CDC reaction has been successfully extended to a larger number of diamine-monoboranes (4-7) and to one amine-borane alcohol precursor (8). The corresponding NB(H)N- and NB(H)O-containing cyclic diaminoboranes (12-15) and oxazaborolidine (16) were obtained in good to high yields. Multiple substitution patterns on the starting amine-borane substrates were evaluated and the reaction was also performed with chiral substrates. Efforts have been spent to understand the mechanism of the ruthenium CDC process. In addition to a computational approach, a strategy enabling the kinetic discrimination on successive events of the catalytic process leading to the formation of the NB(H)N linkage was performed on the six-carbon chain diamine-monoborane 21 and completed with a (15) N NMR study. The long-life bis-σ-borane ruthenium...
Coordination Chemistry Reviews, 2008
NMR has played a major role in the characterization of dihydrogen complexes and a number of polyh... more NMR has played a major role in the characterization of dihydrogen complexes and a number of polyhydrides have been reformulated as dihydrogen complexes on the basis of NMR data. If dihydrogen complexes remain the most widely studied class of σ-complexes, silane compounds are also well recognized as an important family of σ-complexes and more recently a few σ-borane compounds have
Journal of the American Chemical Society, Jan 18, 2007
Journal of the Chemical Society, Chemical Communications, 1993
... Adducts Gilles Alcaraz, Robert Reed, Antoine Baceiredo and Guy Bertrand" Laboratoire... more ... Adducts Gilles Alcaraz, Robert Reed, Antoine Baceiredo and Guy Bertrand" Laboratoire de Chimie de Coordination du CNRS, 205, route de Narbonne, 31077 Toulouse Cedex, France ... go%).? Downloaded by google on 24 April 2011 ...
Organometallics, 2010
ABSTRACT The coordination chemistry of diisopropylaminoborane H2B−NiPr2 with valence isoelectroni... more ABSTRACT The coordination chemistry of diisopropylaminoborane H2B−NiPr2 with valence isoelectronic metal fragments to form, essentially isostructural, [MH2(η2:η2-H2B−NiPr2)(PCy3)2]n+ (M = Ru, n = 0; Rh and Ir, n = 1) has been explored by a combination of X-ray crystallography, NMR spectroscopy, and computational techniques. In the solid state and solution the aminoborane interacts with the metal centers through one four-center four-electron interaction, forming bis(σ-B−H) complexes. The structural data point to tighter interactions between both the Ru and Ir congeners compared to the Rh with significantly shorter M···B distances in the first two. These tighter interactions are mirrored in the spectroscopic data, with the Ru and Ir complexes showing more deshielded 11B chemical shifts and 1H M−H−B resonances that are more shielded than observed for the rhodium complex. Analysis of the bonding between metal and borane using the NBO approach is in very good agreement with the variations in the geometrical and spectroscopic parameters. There is overall a stronger interaction between the borane and the metal fragment for neutral Ru compared to cationic Rh, with cationic Ir in an intermediate situation.
Organic Letters, 2006
A series of new dispiro[fluorene-9′,6,9′′,12-indeno[1,2b]fluorenes] (DSFIFs) that combine indenof... more A series of new dispiro[fluorene-9′,6,9′′,12-indeno[1,2b]fluorenes] (DSFIFs) that combine indenofluorene (IF) and spirobifluorene (SBF) architectural specificities have been prepared. Their anodic oxidations lead to the formation of nonsoluble transparent polymers. The photophysical and electrochemical properties of these new molecules have been evaluated for further blue OLED applications.
Journal of the American Chemical Society, 2008
Starting from RuHCl(H2)(PCy3)2, a terminal ruthenium mesitylborylene complex was obtained via dou... more Starting from RuHCl(H2)(PCy3)2, a terminal ruthenium mesitylborylene complex was obtained via double B-H bond activation of mesitylborane and concomitant release of dihydrogen, such a process being remarkably reversible.
Journal of the American Chemical Society, 2007
... Gilles Alcaraz,* Eric Clot,* Ulrike Helmstedt, Laure Vendier, and Sylviane Sabo-Etien... more ... Gilles Alcaraz,* Eric Clot,* Ulrike Helmstedt, Laure Vendier, and Sylviane Sabo-Etienne* . ... 13) Crestani, MG; Muñoz-Hernández, M.; Arévalo, A.; Acosta-Ramírez, A.; García, JJ J. Am. Chem. Soc.2005, 127, 18066−18073. ...
Journal of Organometallic Chemistry, 2009
The reaction of tert-butylborane with the bis(dihydrogen) complex RuH2(η2-H2)2(PCy3)2 leads to th... more The reaction of tert-butylborane with the bis(dihydrogen) complex RuH2(η2-H2)2(PCy3)2 leads to the corresponding bis σ-borane complex which is the first example of a monoalkylborane ruthenium bis σ-complex. An alternative route involves the reaction of RuHCl(η2-H2)(PCy3)2 with lithium tert-butylborohydride.
Journal of Organometallic Chemistry, 2005
Stereospecific Palladium-Catalyzed Borylation Reaction of 1-Alkenyl Halides with Diispropylaminob... more Stereospecific Palladium-Catalyzed Borylation Reaction of 1-Alkenyl Halides with Diispropylaminoborane. -(EUZENAT, L.; HORHANT, D.; BRIELLES, C.; ALCARAZ*, G.; VAULTIER, M.; J.
Journal of Materials Chemistry, 2008
Inorganic Chemistry, 1996
The structure of P,P-bis(diisopropylamino)-4-phenyl-1,3,2lambda(5)-diazaphosphete, 1a, has been d... more The structure of P,P-bis(diisopropylamino)-4-phenyl-1,3,2lambda(5)-diazaphosphete, 1a, has been determined by a single-crystal X-ray diffraction study (C(19)H(33)N(4)P, monoclinic system, space group P2(1), a = 9.482(1) Å, b = 11.374(3) Å, c = 9.668(2) Å, beta = 97.16(1) degrees, Z = 2). According to quantum chemical calculations at an RHF level of optimization utilizing the 6-31g(d,p) basis set, 1a has a zwitterionic structure with the negative charge delocalized on the NCN allylic fragment and the positive charge localized at the phosphorus. Heterocycle 1a reacts with water and benzaldehyde affording N-phosphoranylbenzamidine 3 (95% yield) and the expected aza-Wittig adduct 4 (85% yield), respectively. Addition of 1 equiv of methyl trifluoromethanesulfonate and of 2 equiv of BH(3).THF to 1a affords cyclic phosphonium salt 5 (94% yield) and the bis(borane) adduct 6a (90% yield), respectively. Dimethyl acetylenedicarboxylate slowly reacts with 1a giving rise to 1,3,4lambda(5)-diazaphosphinine, 9, in 70% yield. The X-ray crystal structures of products 2,3, and 6a are reported (2: C(26)H(38)N(5)P, monoclinic system, space group C2/c, a = 16.337(8) Å, b = 19.810(2) Å, c = 8.800(2) Å, beta = 117.68(2) degrees, Z = 4. 3: C(19)H(35)N(4)OP, orthorhombic system, space group P2(1)2(1)2(1), a = 9.090(1) Å, b = 12.955(2) Å, c = 17.860(3) Å, Z = 4. 6a: C(19)H(39)B(2)N(4)P, orthorhombic system, space group P2(1)2(1)2(1), a = 10.340(1) Å, b = 13.247(1) Å, c = 16.996(1) Å, Z = 4).
Dalton Transactions, 2013
The reactivity of the amino(cyano)borane (i)Pr(2)NBH(CN) (2) towards [RuH(2)(η(2)-H(2))(2)(PCy(3)... more The reactivity of the amino(cyano)borane (i)Pr(2)NBH(CN) (2) towards [RuH(2)(η(2)-H(2))(2)(PCy(3))(2)] (3) was investigated. Our study reveals that the formation of the bis(isocyanoborane) ruthenium complex [RuH(CN)(CN-BHN(i)Pr(2))(2)(PCy(3))(2)] (6) occurs via the intermediacy of the bis(σ-B-H) ruthenium complex [RuH(CN)(H(2)BN(i)Pr(2))(PCy(3))(2)] (5). This transformation involves BCN linkage isomerisation in 2. The diisopropylaminoborane ligand in 5 can be displaced to ultimately produce the bis(σ-borane) complex [RuH(2)(η(2):η(2)-H(2)BN(i)Pr(2))(PCy(3))(2)] (4) as a by-product.
Chemistry - A European Journal, 2007
Chemical Communications, 2009
The stoichiometric reaction of [Rh(COD)Cl](2) with the anion resulting from the deprotonation of ... more The stoichiometric reaction of [Rh(COD)Cl](2) with the anion resulting from the deprotonation of dppm(BH(3))(2) yielded a new alkyl Rh(I) complex; the coordination modes of the BH(3) groups are discussed on the basis of X-ray data, variable temperature multinuclear NMR experiments and DFT studies.
Chemical Communications, 2003
A series of octupolar molecules derived from the boroxine framework were designed and their optic... more A series of octupolar molecules derived from the boroxine framework were designed and their optical nonlinearities were investigated by performing harmonic light scattering experiments in solution; the molecules were found to combine excellent transparency in the near UV-visible region (lambdamax < or = 280 nm) and significant first-order hyperpolarisabilities (up to beta(0) = 56 x 10(-30) esu).
Chemical Communications, 2010
A novel cascade of reactions is designed to control in situ the deposition of noble metal islands... more A novel cascade of reactions is designed to control in situ the deposition of noble metal islands (e.g. Rh) on top of nanoparticles of a 3d metal (e.g. Fe, Co).
Chemical Communications, 2003
Thermal decomposition of hindered amine-borane adducts leads in high yields to monomeric (dialkyl... more Thermal decomposition of hindered amine-borane adducts leads in high yields to monomeric (dialkylamino)boranes R1R2N-BH2 (R1 and R2 = alkyl) that are new and efficient boron-sources in the Pd0 catalyzed borylation reaction affording monomeric aryl(dialkylamino)boranes R1R2N-BHR3 (R3 = aryl).