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Therrien, Bruno

Nom
Therrien, Bruno
Affiliation principale
Fonction
Professeur titulaire
Email
bruno.therrien@unine.ch
Identifiants
https://libra.unine.ch/handle/123456789/382
_
0000-0002-0388-2745

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  • Publication
    Accès libre
    Synthesis, molecular structure and cytotoxicity of molecular materials based on water soluble half-sandwich Rh(III) and Ir(III) tetranuclear metalla-cycles
    (2013)
    Gupta, Gajendra
    ;
    Murray, Benjamin S.
    ;
    Dyson, Paul J.
    ;
    Therrien, Bruno 
    The neutral dinuclear complexes [(?5-C5Me5)2Rh2(?-dhnq)Cl2] (1) and [(?5-C5Me5)2Ir2(?-dhnq)Cl2] (2) (dhnqH2 = 5,8-dihydroxy-1,4-naphthoquinone) were obtained from the reaction of [(?5-C5Me5)M(?-Cl)Cl]2 (M = Rh, Ir) with dhnqH2 in the presence of CH3COONa. Treatment of 1 or 2 in methanol with linear ditopic ligands L (L = pyrazine, 4,4'-bipyridine or 1,2-bis(4-pyridyl)ethylene), in the presence of AgCF3SO3, affords the corresponding tetranuclear metalla-rectangles [(?5-C5Me5)4M4(?-dhnq)2(?-L)2]4+ (L = pyrazine, M = Rh, 3; M = Ir, 4; L = 4,4'-bipyridine, M = Rh, 5; M = Ir, 6; L = 1,2-bis(4-pyridyl)ethylene, M = Rh, 7; M = Ir, 8). All complexes were isolated as their triflate salts and were fully characterized by IR, 1H and 13C NMR spectroscopy, and some representative complexes by single-crystal X-ray structure anal. The X-ray structures of 3, 5 and 6 confirm the formation of the tetranuclear metalla-cycles, and suggest that complexes 5 and 6 possess a cavity of sufficient size to encapsulate small guest mols. In addn., the antiproliferative activity of the metalla-cycles 3-8 was evaluated against the human ovarian A2780 (cisplatin sensitive) and A2780cisR (cisplatin resistant) cancer cell lines and on non-tumorigenic human embryonic kidney HEK293 cells. All cationic tetranuclear metalla-rectangles were found to be highly cytotoxic, with IC50 values in the low micromolar range. [on SciFinder(R)]
  • Publication
    Accès libre
    Study of complexes of platinum group metals containing nitrogen bases derived from pyridine aldehydes: Interesting molecular structures with unpredicted bonding modes of the ligands
    (2011)
    Gupta, Gajendra
    ;
    Gloria, Sairem
    ;
    Nongbri, Saphidabha. L.
    ;
    Therrien, Bruno 
    ;
    Rao, Kollipara Mohan
    A 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.
  • Publication
    Accès libre
    Study of half sandwich platinum group metal complexes containing tetradentate N-donor ligand bearing two di-pyridylamine units linked by an aromatic spacer
    (2011)
    Gupta, Gajendra
    ;
    Sairem, Gloria
    ;
    Therrien, Bruno 
    ;
    Babulal, Das
    ;
    Rao, Kollipara Mohan
    A general approach for the preparation of dinuclear η5- and η6-cyclic hydrocarbon platinum group metal complexes, viz. [(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), bearing the bis-bidentate ligand 1,2-bis(di-2-pyridylaminomethyl)benzene (NN∩NN), which contains two chelating di-pyridylamine units connected by an aromatic spacer, is reported. The cationic dinuclear complexes have been isolated as their hexafluorophosphate or hexafluoroantimonate salts and characterized by use of a combination of NMR, IR and UV–vis spectroscopic methods and by mass spectrometry. The solid state structure of three derivatives, [2][SbF6]2, [3][PF6]2 and [4][PF6]2, has been determined by X-ray structure analysis.
  • Publication
    Accès libre
    [Bis(2-pyridyl-κN)amine]chlorido(η6-hexamethylbenzene)ruthenium(II) hexafluoridophosphate dichloromethane solvate
    (2011)
    Gupta, Gajendra
    ;
    Therrien, Bruno 
    ;
    Kim, Jinkwom
    In the title half-sandwich complex, [RuCl(η6-C12H18)(C10H9N3)]PF6•CH2Cl2, the ruthenium(II) ion is four-coordinated by a chloro, a hexamethylbenzene and a bidentate N, N'-chelating di(pyridin-2-yl)amine ligand. In the crystal, the amino N-H group forms a hydrogen bond with the chloro ligand of a neighbouring complex, thus forming chains along the b axis. Weak intermolecular C-H...F and C-H... Cl contacts are also observed.
  • Publication
    Accès libre
    Half sandwich platinum group metal complexes containing tetradentate N-donor ligand bearing two pyrazolyl-pyridine units linked by an aromatic spacer
    (2010)
    Gupta, Gajendra
    ;
    Therrien, Bruno 
    ;
    Rao, Kollipara Mohan
    Reaction 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.
  • Publication
    Accès libre
    Study of novel η5-cyclopentadienyl and η6-arene platinum group metal complexes containing a N4-type ligand and their structural characterization
    (2009)
    Gupta, Gajendra
    ;
    Yap, Glenn P.A.
    ;
    Therrien, Bruno 
    ;
    Rao, Kollipara Mohan
    The 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.