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Süss-Fink, Georg
Nom
Süss-Fink, Georg
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Professeur ordinaire
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georg.suess-fink@unine.ch
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- PublicationAccès libreArene ruthenium bis-saccharinato complexes: Synthesis, molecular structure and catalytic oxidation properties in aqueous solutionArene ruthenium complexes [(η6-arene)Ru(sacc)2(OH2)] (arene = para-cymeme, benzene) containing an aqua and two saccharinato ligands have been synthesized from [(η6-arene)RuCl2]2 and sodium saccharinate in a water-ethanol mixture (1:1). The aqua complex [(η6-MeC6H4Pri)Ru(sacc)2(OH2)] reacts with acetonitrile to give the acetonitrile complex [(η6-MeC6H4Pri)Ru(sacc)2(NCMe)]. The corresponding benzene derivative [(η6-C6H6)Ru(sacc)2(NCMe)] was obtained from [(η6-C6H6)RuCl2]2 and saccNa in an acetonitrile-methanol mixture (1:1). All new complexes show a piano-stool geometry with two mono-hapto nitrogen-bonded saccharinato ligands in addition to a H2O or MeCN ligand. All complexes of the type [(η6-arene)Ru(sacc)2(OH2)] and [(η6-arene)Ru(sacc)2(NCMe)] were found to catalyze the oxidation of secondary alcohols with tert-butyl hydroperoxide (ButOOH) to give the corresponding ketones in aqueous solution.
- PublicationAccès libreBimetallic ruthenium–tin chemistry: Synthesis and molecular structure of arene ruthenium complexes containing trichlorostannyl ligands(2010)
; ;Thai, Trieu-Tien; ; ;Shapovalov, Sergey S. ;Pasynskii, Alexandr A.Plasseraud, LaurentA series of neutral, anionic and cationic arene ruthenium complexes containing the trichlorostannyl ligand have been synthesised from SnCl2 and the corresponding arene ruthenium dichloride dimers [(η6-arene)Ru(μ2-Cl)Cl]2 (arene = C6H6, PriC6H4Me). While the reaction with triphenylphosphine and stannous chloride only gives the neutral mono(trichlorostannyl) complexes [(η6-C6H6)Ru(PPh3)(SnCl3)Cl] (1) and [(η6-PriC6H4Me)Ru(PPh3)(SnCl3)Cl] (2), the neutral di(trichlorostannyl) complex [(η6-PriC6H4Me)Ru(NCPh)(SnCl3)2] (3) could be obtained for the para-cymene derivative with benzonitrile as additional ligand. By contrast, the analogous reaction with the benzene derivative leads to a salt composed of the cationic mono(trichlorostannyl) complex [(η6-C6H6)Ru(NCPh)2(SnCl3)]+ (5) and of the anionic tris(trichlorostannyl) complex [(η6-C6H6)Ru(SnCl3)3]− (6). On the other hand, [(η6-PriC6H4Me)Ru(μ2-Cl)Cl]2 reacts with SnCl2 and hexamethylenetetramine hydrochloride or 18-crown-6 to give the anionic di(trichlorostannyl) complex [(η6-PriC6H4Me)Ru(SnCl3)2Cl]− (4), isolated as the hexamethylenetetrammonium salt or the chloro-tin 18-crown-6 salt. The single-crystal X-ray structure analyses of 1, 2, [(CH2)6N4H][4], [(18-crown-6)SnCl][4] and [5][6] reveal for all complexes a pseudo-tetrahedral piano-stool geometry with ruthenium–tin bonds ranging from 2.56 (anionic complexes) to 2.60 Å (cationic complex). - PublicationAccès libreArene ruthenium oxinato complexes: Synthesis, molecular structure and catalytic activity for the hydrogenation of carbon dioxide in aqueous solutionTwo families of arene ruthenium oxinato complexes of the types [(η6-arene)Ru(η2-N,O-L)Cl] and [(η6-arene)Ru(η2-N,O-L)(OH2)]+ have been synthesized from the dinuclear precursors [(η6-arene)RuCl2]2 (arene = para-cymeme or hexamethylbenzene) and the corresponding oxine LH (LH = 8-hydroxyquinoline, 5-chloro-8-hydroxyquinoline, 5,7-dichloro-8-hydroxyquinoline, 5-nitro-8-hydroxyquinoline, 5,7-dimethyl-8-hydroxyquinoline, 5,7-dichloro-2-methyl-8-hydroxyquinoline). The molecular structures of the neutral chloro complexes [(η6-C6Me6)Ru(η2-N,O-L)Cl] (LH = 8-hydroxyquinoline, 5,7-dichloro-2-methyl-8-hydroxyquinoline) and [(η6-MeC6H4Pri)Ru(η2-N,O-L)Cl] (LH = 5,7-dichloro-2-methyl-8-hydroxyquinoline) as well as those of the cationic aqua derivatives [(η6-MeC6H4Pri)Ru(η2-N,O-L)(OH2)]+ (LH = 8-hydroxyquinoline, 5,7-dimethyl-8-hydroxyquinoline), isolated as the tetrafluoroborate salts, show in all cases a piano-stool arrangement with the arene ligand, the chelating oxinato ligand and the chloro or the aqua ligand surrounding the ruthenium center in a pseudo-tetrahedral fashion. The analogous reaction of [(η6-MeC6H4Pri)RuCl2]2 with other N,O-chelating ligands such as 2-pyridinemethanol or tetrahydrofurfurylamine did not give the expected analogs but resulted in the formation of the complexes [(η6-MeC6H4Pri)Ru(η2-NC5H4CH2OH)Cl]+ and [(η6-MeC6H4Pri)Ru(η1-NHCH2C4H3O)Cl2]. The neutral and cationic complexes of the types [(η6-arene)Ru(η2-N,O-L)Cl] and [(η6-arene)Ru(η2-N,O-L)(OH2)]+ have been found to catalyze the hydrogenation of carbon dioxide to give formate in alkaline aqueous solution with catalytic turnovers up to 400.