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Therrien, Bruno
Nom
Therrien, Bruno
Affiliation principale
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Professeur titulaire
Email
bruno.therrien@unine.ch
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Résultat de la recherche
Voici les éléments 1 - 10 sur 11
- PublicationMétadonnées seulementReactivity study of arene(azido)ruthenium N-O-base complexes with activated alkynes(2011)
; Rao, Kollipara MohanSubstitution reactions of chloro ?6-arene ruthenium N-O-base complexes [(?6-arene)Ru(N-O)Cl] [N-O = pyrazine-2-carboxylic acid (pca-H), 8-hydroxyquinoline (hq-H); arene = p-iPrC6H4Me, N-O = hq (1); arene = C6Me6, N-O = hq (2)] with NaN3 yield neutral arene ruthenium azido complexes [(?6-arene)Ru(N-O)N3] [N-O = pca, arene = p-iPrC6H4Me (3), arene = C6Me6 (4); N-O = hq, arene = p-iPrC6H4Me (5), arene = C6Me6 (6)]. These complexes undergo [3 + 2] dipolar cycloaddns. with the activated alkynes di-Me and di-Et acetylenedicarboxylate to yield the arene triazole complexes [(?6-arene)Ru(N-O){N3C2(CO2R)2}] [N-O = pca, R = Me, arene = p-iPrC6H4Me (7), C6Me6 (8); R = Et, arene = p-iPrC6H4Me (9), C6Me6 (10); N-O = hq, R = Me, arene = p-iPrC6H4Me (11) C6Me6 (12); R = Et, arene = p-iPrC6H4Me (13), C6Me6 (14)]. On the basis of a proton NMR study, the adducts of ruthenium N-O-base complexes with di-Me acetylenedicarboxylate are assigned as the N(2) isomers while the adducts with di-Et acetylenedicarboxylate are assigned as the N(1) isomers. All complexes have been characterized by IR and NMR spectroscopy as well as by elemental anal. The structures of the azido complexes [(?6-p-iPrC6H4Me)Ru(pca)N3] (3), [(?6-p-iPrC6H4Me)Ru(hq)N3] (5) and [(?6-C6Me6)Ru(hq)N3] (6) were detd. by single crystal X-ray diffraction. [on SciFinder(R)] - PublicationAccès libreStudy of complexes of platinum group metals containing nitrogen bases derived from pyridine aldehydes: Interesting molecular structures with unpredicted bonding modes of the ligands(2011)
; Rao, Kollipara MohanA series of mono-cationic dinuclear half sandwich ruthenium, rhodium and iridium metal complexes have been synthesized using ((pyridin-2-yl)methylimino)nicotinamide (L1) and ((picolinamido)phenyl)picolinamide (L2) ligands: [(η6-arene)2Ru2 (μ-L1)Cl3]+ (arene = C6H6, 1; p-iPrC6H4Me, 2; C6Me6, 3), [(η5-C5Me5)2M2(μ-L1)Cl3] + (M = Rh, 4; Ir, 5), and [(η6-arene)2Ru2(μ-L2)(μ-Cl)]+ (arene = C6H6, 6; p-iPrC6H4Me, 7; C6Me6, 8), [(η5-C5Me5)2M2(μ-L2)Cl2]+ (M = Rh, 9; Ir, 10). All the complexes have been isolated as their hexafluorophosphate salts and fully characterized by use of a combination of NMR and IR spectroscopy. The solid state structure of three representatives 4, 6 and 9 has been determined by X-ray crystallographic studies. Interestingly, in the molecular structure of 4, the first metal is bonded to two nitrogen atoms whereas the second metal center is coordinated to only one nitrogen atom with two terminal chloride ligands. Fascinatingly in the case of the complexes with the symmetrical ligand L2, both ruthenium centers having η6-arene groups are bonded to nitrogen atoms with a bridging chloride atom between the two metal centers, whereas the metals with η5-Cp∗ groups are bonded to the ligand N,O and N,N fashion. - PublicationAccès libreStudy of half sandwich platinum group metal complexes containing tetradentate N-donor ligand bearing two di-pyridylamine units linked by an aromatic spacer(2011)
; - PublicationAccès libreHalf sandwich platinum group metal complexes containing tetradentate N-donor ligand bearing two pyrazolyl-pyridine units linked by an aromatic spacer(2010)
; Rao, Kollipara MohanReaction of the bis-bidentate ligand, 1,3-bis((3-(pyridin-2-yl)-1H-pyrazol-1-yl)methyl)benzene (NN∩NN), containing two chelating pyrazolyl-pyridine units connected by an aromatic spacer with platinum group metal complexes results in a series of cationic binuclear complexes, [(η6-arene)2Ru2(NN∩NN)Cl2]2+ (arene = C6H6, 1; p-iPrC6H4Me, 2; C6Me6, 3), [(η5-C5Me5)2M2(NN∩NN)Cl2]2+ (M = Rh, 4; Ir, 5), [(η5-C5H5)2M2(NN∩NN)(PPh3)2]2+ (M = Ru, 6; Os, 7), [(η5-C5Me5)2Ru2(NN∩NN)(PPh3)2]2+ (8) and [(η5-C9H7)2Ru2(NN∩NN)(PPh3)2]2+ (9). All these complexes have been isolated as their hexafluorophosphate salts and fully characterized by use of a combination of NMR spectroscopy, IR spectroscopy and mass spectrometry. The solid state structures of three complexes, [2][PF6]2, [4][PF6]2 and [6][PF6]2, has been determined by X-ray crystallographic studies. - PublicationAccès libreMono and dinuclear half-sandwich platinum group metal complexes bearing pyrazolyl-pyrimidine ligands: Syntheses and structural studies(2010)
; - PublicationAccès libreSyntheses and characterization of mono and dinuclear complexes of platinum group metals bearing benzene-linked bis(pyrazolyl)methane ligands(2010)
; Rao, Kollipara MohanReaction of the benzene-linked bis(pyrazolyl)methane ligands, 1,4-bis{bis(pyrazolyl)-methyl}benzene (L1) and 1,4-bis{bis(3-methylpyrazolyl)methyl}benzene (L2), with pentamethylcyclopentadienyl rhodium and iridium complexes [(η5-C5Me5)M(μ-Cl)Cl]2 (M = Rh and Ir) in the presence of NH4PF6 results under stoichiometric control in both, mono and dinuclear complexes, [(η5-C5Me5)RhCl(L)]+ {L = L1 (1); L2 (2)}, [(η5-C5Me5)IrCl(L)]+ {L = L1 (3); L2 (4)} and [{(η5-C5Me5)RhCl}2(μ-L)]2+ {L = L1 (5); L2 (6)}, [{(η5-C5Me5)IrCl}2(μ-L)]2+ {L = L1 (7); L2 (8)}. In contrast, reaction of arene ruthenium complexes [(η6Âarene)Ru(μ-Cl)Cl]2 (arene = C6H6, p-iPrC6H4Me and C6Me6) with the same ligands (L1 or L2) gives only the dinuclear complexes [{(η6-C6H6)RuCl}2(μ-L)]2+ {L = L1 (9); L2 (10)}, [{(η6-p-iPrC6H4Me)RuCl}2 (μ-L)]2+ {L = L1 (11); L2 (12)} and [{(η6-C6Me6)RuCl}2(μ-L)]2+ {L = L1 (13); L2 (14)}. All complexes were isolated as their hexafluorophosphate salts. The single-crystal X-ray crystal structure analyses of [7](PF6)2, [9](PF6)2 and [11](PF6)2 reveal a typical piano-stool geometry around the metal centers with six-membered metallo-cycle in which the 1,4-bis{bis(pyrazolyl)-methyl}benzene acts as a bis-bidentate chelating ligand. - PublicationAccès libreMono and dinuclear complexes of half-sandwich platinum group metals (Ru, Rh and Ir) bearing a flexible pyridyl-thiazole multidentate donor ligand(2010)
; Rao, Kollipara MohanThe mononuclear cationic complexes [(η6-C6H6)RuCl(L)]+ (1), [(η6-p-iPrC6H4Me)RuCl(L)]+ (2), [(η5-C5H5)Ru(PPh3)(L)]+ (3), [(η5-C5Me5)Ru(PPh3)(L)]+ (4), [(η5-C5Me5)RhCl(L)]+ (5), [(η5-C5Me5)IrCl(L)]+ (6) as well as the dinuclear dicationic complexes [{(η6-C6H6)RuCl}2 (L)]2+ (7), [{(η6-p-iPrC6H4Me)RuCl}2 (L)]2+ (8), [{(η5-C5H5)Ru(PPh3)}2 (L)]2+ (9), [{(η5-C5Me5)Ru(PPh3)}2 (L)]2+ (10), [{(η5-C5Me5)RhCl}2 (L)]2+ (11) and [{(η5-C5Me5)IrCl}2 (L)]2+ (12) have been synthesized from 4,4′-bis(2-pyridyl-4-thiazole) (L) and the corresponding complexes [(η6-C6H6)Ru(μ-Cl)Cl]2, [(η6-p-iPrC6H4Me)Ru(μ-Cl)Cl]2, [(η5-C5H5)Ru(PPh3)2Cl)], [(η5-C5Me5)Ru(PPh3)2Cl], [(η5-C5Me5)Rh(μ-Cl)Cl]2 and [(η5-C5Me5)Ir(μ-Cl)Cl]2, respectively. All complexes were isolated as hexafluorophosphate salts and characterized by IR, NMR, mass spectrometry and UV–vis spectroscopy. The X-ray crystal structure analyses of [3]PF6, [5]PF6, [8](PF6)2 and [12](PF6)2 reveal a typical piano-stool geometry around the metal centers with a five-membered metallo-cycle in which 4,4′-bis(2-pyridyl-4-thiazole) acts as a N,N′-chelating ligand. - PublicationMétadonnées seulementMono and dinuclear complexes of half-sandwich platinum group metals (Ru, Rh and Ir) bearing a flexible pyridyl-thiazole multidentate donor ligand(2009)
; Rao, Kollipara MohanThe mononuclear cationic complexes [(?6-C6H6)RuCl(L)]+ (1, L = 2,2'-bis(2-pyridyl)-4,4'-bithiazole), [(?6-p-iPrC6H4Me)RuCl(L)]+ (2), [(?5-C5H5)Ru(PPh3)(L)]+ (3), [(?5-C5Me5)Ru(PPh3)(L)]+ (4), [(?5-C5Me5)RhCl(L)]+ (5), [(?5-C5Me5)IrCl(L)]+ (6) as well as the dinuclear dicationic complexes [{(?6-C6H6)RuCl}2(L)]2+ (7), [{(?6-p-iPrC6H4Me)RuCl}2(L)]2+ (8), [{(?5-C5H5)Ru(PPh3)}2(L)]2+ (9), [{(?5-C5Me5)Ru(PPh3)}2(L)]2+ (10), [{(?5-C5Me5)RhCl}2(L)]2+ (11) and [{(?5-C5Me5)IrCl}2(L)]2+ (12) were synthesized from 2,2'-bis(2-pyridyl)-4,4'-bithiazole (L) and the corresponding complexes [(?6-C6H6)Ru(?-Cl)Cl]2, [(?6-p-iPrC6H4Me)Ru(?-Cl)Cl]2, [(?5-C5H5)Ru(PPh3)2Cl], [(?5-C5Me5)Ru(PPh3)2Cl], [(?5-C5Me5)Rh(?-Cl)Cl]2 and [(?5-C5Me5)Ir(?-Cl)Cl]2, resp. All complexes were isolated as hexafluorophosphate salts and characterized by IR, NMR, mass spectrometry and UV-visible spectroscopy. The x-ray crystal structure analyses of [3]PF6, [5]PF6, [8](PF6)2 and [12](PF6)2 reveal a typical piano-stool geometry around the metal centers with a five-membered metallo-cycle in which 2,2'-bis(2-pyridyl)-4,4'-bithiazole acts as a N,N'-chelating ligand. [on SciFinder(R)] - PublicationMétadonnées seulementStudy of novel ?5-cyclopentadienyl and ?6-arene platinum group metal complexes containing a N4-type ligand and their structural characterization(2009)
; Rao, Kollipara MohanThe mononuclear ?5-cyclopentadienyl complexes [(?5-C5H5)Ru(PPh3)2Cl], [(?5-C5H5)Os(PPh3)2Br] and pentamethylcyclopentadienyl complex [(?5-C5Me5)Ru(PPh3)2Cl] react in the presence of 1 equiv. of the tetradentate N,N'-chelating ligand 3,5-bis(2-pyridyl)pyrazole (bpp-H) and 1 equiv. of NH4PF6 in methanol to afford the mononuclear complexes [(?5-C5H5)Ru(PPh3)(bpp-H)]PF6 ([1]PF6), [(?5-C5H5)Os(PPh3)(bpp-H)]PF6 ([2]PF6) and [(?5-C5Me5)Ru(PPh3)(bpp-H)]PF6 ([3]PF6), resp. The dinuclear ?5-pentamethylcyclopentadienyl complexes [(?5-C5Me5)Rh(?-Cl)Cl]2 and [(?5-C5Me5)Ir(?-Cl)Cl]2 as well as the dinuclear ?6-arene ruthenium complexes [(?6-C6H6)Ru(?-Cl)Cl]2 and [(?6-p-iPrC6H4Me)Ru(?-Cl)Cl]2 react with 2 equiv. of bpp-H in the presence of NH4PF6 or NH4BF4 to afford the corresponding mononuclear complexes [(?5-C5Me5)Rh(bpp-H)Cl]PF6 ([4]PF6), [(?5-C5Me5)Ir(bpp-H)Cl]PF6 ([5]PF6), [(?6-C6H6)Ru(bpp-H)Cl]BF4 ([6]BF4) and [(?6-p-iPrC6H4Me)Ru(bpp-H)Cl]BF4 ([7]BF4). However, in the presence of 1 equiv. of bpp-H and NH4BF4 the reaction with the same ?6-arene ruthenium complexes affords the dinuclear salts [(?6-C6H6)2Ru2(bpp)Cl2]BF4 ([8]BF4) and [(?6-p-iPrC6H4Me)2Ru2(bpp)Cl2]BF4 ([9]BF4), resp. These compds. have been characterized by IR, NMR and mass spectrometry, as well as by elemental anal. The mol. structures of [1]PF6, [5]PF6 and [8]BF4 have been established by single crystal x-ray diffraction studies and some representative complexes have been studied by UV-vis spectroscopy. [on SciFinder(R)] - PublicationAccès libreStudy of novel η5-cyclopentadienyl and η6-arene platinum group metal complexes containing a N4-type ligand and their structural characterization(2009)
; Rao, Kollipara MohanThe mononuclear η5-cyclopentadienyl complexes [(η5-C5H5)Ru(PPh3)2Cl], [(η5-C5H5)Os(PPh3)2Br] and pentamethylcyclopentadienyl complex [(η5-C5Me5)Ru(PPh3)2Cl] react in the presence of 1 eq. of the tetradentate N,N′-chelating ligand 3,5-bis(2-pyridyl)pyrazole (bpp-H) and 1 eq. of NH4PF6 in methanol to afford the mononuclear complexes [(η5-C5H5)Ru(PPh3)(bpp-H)]PF6 ([1]PF6), [(η5-C5H5)Os(PPh3)(bpp-H)]PF6 ([2]PF6) and [(η5-C5Me5)Ru(PPh3)(bpp-H)]PF6 ([3]PF6), respectively. The dinuclear η5-pentamethylcyclopentadienyl complexes [(η5-C5Me5)Rh(μ-Cl)Cl]2 and [(η5-C5Me5)Ir(μ-Cl)Cl]2 as well as the dinuclear η6-arene ruthenium complexes [(η6-C6H6)Ru(μ-Cl)Cl]2 and [(η6-p-iPrC6H4Me)Ru(μ-Cl)Cl]2 react with 2 eq. of bpp-H in the presence of NH4PF6 or NH4BF4 to afford the corresponding mononuclear complexes [(η5-C5Me5)Rh(bpp-H)Cl]PF6 ([4]PF6), [(η5-C5Me5)Ir(bpp-H)Cl]PF6 ([5]PF6), [(η6-C6H6)Ru(bpp-H)Cl]BF4 ([6]BF4) and [(η6-p-iPrC6H4Me)Ru(bpp-H)Cl]BF4 ([7]BF4). However, in the presence of 1 eq. of bpp-H and NH4BF4 the reaction with the same η6-arene ruthenium complexes affords the dinuclear salts [(η6-C6H6)2Ru2 (bpp)Cl2]BF4 ([8]BF4) and [(η6-p-iPrC6H4Me)2Ru2 (bpp)Cl2]BF4 ([9]BF4), respectively. These compounds have been characterized by IR, NMR and mass spectrometry, as well as by elemental analysis. The molecular structures of [1]PF6, [5]PF6 and [8]BF4 have been established by single crystal X-ray diffraction studies and some representative complexes have been studied by UV–vis spectroscopy.