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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
    Mono and dinuclear complexes of half-sandwich platinum group metals (Ru, Rh and Ir) bearing a flexible pyridyl-thiazole multidentate donor ligand
    (2010)
    Prasad, Kota Thirumala
    ;
    Therrien, Bruno 
    ;
    Rao, Kollipara Mohan
    The 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.
  • Publication
    Accès libre
    Syntheses and characterization of mono and dinuclear complexes of platinum group metals bearing benzene-linked bis(pyrazolyl)methane ligands
    (2010)
    Prasad, Kota Thirumala
    ;
    Therrien, Bruno 
    ;
    Rao, Kollipara Mohan
    Reaction 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 [(η6­arene)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.
  • Publication
    Accès libre
    Mono and dinuclear half-sandwich platinum group metal complexes bearing pyrazolyl-pyrimidine ligands: Syntheses and structural studies
    (2010)
    Prasad, Kota Thirumala
    ;
    Therrien, Bruno 
    ;
    Geib, Steven
    ;
    Rao, Kollipara Mohan
    Reactions of 0.5 eq. of the dinuclear complexes [(η6-arene)Ru(μ-Cl)Cl]2 (arene = η6-C6H6, η6-p-iPrC6H4Me) and [(Cp∗)M(μ-Cl)Cl]2 (M = Rh, Ir; Cp∗ = η5-C5Me5) with 4,6-disubstituted pyrazolyl-pyrimidine ligands (L) viz. 4,6-bis(pyrazolyl)pyrimidine (L1), 4,6-bis(3-methyl-pyrazolyl)pyrimidine (L2), 4,6-bis(3,5-dimethyl-pyrazolyl)pyrimidine (L3) lead to the formation of the cationic mononuclear complexes [(η6-C6H6)Ru(L)Cl]+ (L = L1, 1; L2, 2; L3, 3), [(η6-piPrC6H4Me)Ru(L)Cl]+ (L = L1, 4; L2, 5; L3, 6), [(Cp∗)Rh(L)Cl]+ (L = L1, 7; L2, 8; L3, 9) and [(Cp∗)Ir(L)Cl]+ (L = L1, 10; L2, 11; L3, 12), while reactions with 1.0 eq. of the dinuclear complexes [(η6-arene)Ru(μ-Cl)Cl]2 and [(Cp∗)M(μ-Cl)Cl]2 give rise to the dicationic dinuclear complexes [{(η6-C6H6)RuCl}2(L)]2+ (L = L1, 13; L2, 14; L3, 15), [{(η6-p-iPrC6H4Me)RuCl}2(L)]2+ (L = L1, 16; L2, 17; L3, 18), [{(Cp∗)RhCl}2(L)]2+ (L = L1, 19; L2, 20; L3, 21) and [{(Cp∗)IrCl}2 (L)]2+ (L = L1 22; L2, 23; L3 24). The molecular structures of [3]PF6, [6]PF6, [7]PF6 and [18](PF6)2 have been established by single crystal X-ray structure analysis.
  • 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.