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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, structure and electrochemistry of cationic diruthenium complexes of the type [(N∩N)2Ru2 (CO)2 (μ-CO)2(μ-OOCFc)]+ containing a ferrocenecarboxylato bridge and two chelating aromatic diimine ligands
    (2007)
    Auzias, Mathieu
    ;
    Therrien, Bruno 
    ;
    Süss-Fink, Georg 
    ;
    Štěpnička, Petr
    ;
    Ludvík, Jiří
    The dinuclear bis(ferrocenecarboxylato) complex Ru2 (CO)4 (μ-OOCFc)2 (py)2 (Fc = ferrocenyl, py = pyridine) was found to react with aromatic diimines (2,2′-dipyridyl, 4,4′-dimethyl-2,2′-dipyridyl, 1,10-phenanthroline, 5-nitro-1,10-phenanthroline, and 5-amino-1,10-phenanthroline) in methanol to give the cationic diruthenium complexes [(N∩N)2Ru2 (CO)2 (μ-CO)2(μ-OOCFc)]+ (1: N∩N = 2,2′-dipyridyl, 2: N∩N = 4,4′-dimethyl-2,2′-dipyridyl, 3: N∩N = 1,10-phenanthroline, 4: N∩N = 5-nitro-1,10-phenanthroline, 5: N∩N = 5-amino-1,10-phenanthroline), which have been isolated as the hexafluorophosphate salts. The molecular structure of 3, solved by single-crystal X-ray analysis of the tetraphenylborate salt [3][BPh4], shows a diruthenium backbone bridged by two carbonyl and by one ferrocenecarboxylato ligand, the two 1,10-phenanthroline ligands being in the axial positions. Cyclic voltammetry in dichloromethane reveals for all compounds two successive oxidations due to ferrocene/ferrocenium redox couple and oxidation of the diruthenium core.
  • Publication
    Accès libre
    Mono and dinuclear iridium, rhodium and ruthenium complexes containing chelating carboxylato pyrazine ligands: Synthesis, molecular structure and electrochemistry
    (2007)
    Govindaswamy, Padavattan
    ;
    Therrien, Bruno 
    ;
    Süss-Fink, Georg 
    ;
    Štěpnička, Petr
    ;
    Ludvík, Jiří
    The mononuclear complexes [(η5-C5Me5)IrCl(L1)] (1), [(η5-C5Me5)RhCl(L1)] (2), [(η6-p-PriC6H4Me)RuCl(L1)] (3) and [(η6-C6Me6)RuCl(L1)] (4) have been synthesised from pyrazine-2-carboxylic acid (HL1) and the corresponding complexes [{(η5-C5Me5)IrCl2}2], [{(η5-C5Me5)RhCl2}2], [{(η6-p-PriC6H4Me)RuCl2}2], and [{(η6-C6Me6)RuCl2}2], respectively. The related dinuclear complexes [{(η5-C5Me5)IrCl}2 (μ-L2)] (5), [{(η5-C5Me5)RhCl}2 (μ-L2)] (6), [{(η6-p-PriC6H4Me)RuCl}2 (μ-L2)] (7) and [{(η6-C6Me6)RuCl}2 (μ-L2)] (8) have been obtained in a similar manner from pyrazine-2,5-dicarboxylic acid (H2L2). Compounds isomeric to the latter series, [{(η5-C5Me5)IrCl}2 (μ-L3)] (9), [{(η5-C5Me5)RhCl}2 (μ-L3)] (10), [{(p-PriC6H4Me)RuCl}2 (μ-L3)] (11) and [{(η6-C6Me6)RuCl}2 (μ-L3)] (12), have been prepared by using pyrazine-2,3-dicarboxylic acid (H2L3) instead of H2L2. The molecular structures of 2 and 3, determined by X-ray diffraction analysis, show the pyrazine-2-carboxylato moiety to act as an N,O-chelating ligand, while the structure analyses of 5–7, confirm that the pyrazine-2,5-dicarboxylato unit bridges two metal centres. The electrochemical behaviour of selected representatives has been studied by voltammetric techniques.
  • Publication
    Accès libre
    Dinuclear hexamethylbenzene ruthenium cations containing η1:η2-2-(ferrocenyl)ethen-1-yl ligands: Synthesis, structure, electrochemistry
    (2006)
    Tschan, Mathieu J.-L.
    ;
    Therrien, Bruno 
    ;
    Ludvík, Jiří
    ;
    Štěpnička, Petr
    ;
    Süss-Fink, Georg 
    The cationic ferrocenyl-containing complexes [(η6-C6Me6)2Ru2 (μ-η1:η2-CH–CHFc)2 (μ-H)]+ (3) and [(η6-C6Me6)2Ru2 (μ-PPh2)(μ-η1:η2-CH–CHFc)(μ-H)]+ (4) have been synthesised in ethanol from ethynylferrocene and the dinuclear precursors [(η6-C6Me6)2Ru2 (μ-H)3]+ (1) and [(η6-C6Me6)2Ru2(μ-PPh2)(μ-H)2]+ (2) respectively, and isolated as tetrafluoroborate salts. The spectroscopic data of 3 and 4 as well as the single-crystal X-ray diffraction analysis of [4][BF4] show that the alkyne function of ethynylferrocene has been converted to a σ/π-ethenyl ligand by transfer of a bridging hydride from the diruthenium backbone onto the α-carbon of the triple bond in ethynylferrocene. The ferrocenyl-containing diruthenium compounds [3][BF4] and [4][BF4] as well as their parent compounds [1][BF4] and [2][BF4] have been studied by voltammetric techniques: Whereas 1 shows only an irreversible Ru(II)/Ru(III) oxidation, the phosphido-bridged derivative 2 displays two well-separated one-electron redox processes. In the case of 3 and 4, the ferrocenyl substituents give rise to additional reversible ferrocene/ferrocenium waves.