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  • Publication
    Métadonnées seulement
    Bimetallic ruthenium-tin chemistry: Synthesis and molecular structure of arene ruthenium complexes containing trichlorostannyl ligands
    (2010) ;
    Thai, Trieu-Tien
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    ; ;
    Shapovalov, Sergey S.
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    Pasynskii, Alexandr A.
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    Plasseraud, Laurent
    A series of neutral, anionic and cationic arene ruthenium complexes contg. the trichlorostannyl ligand were synthesized from SnCl2 and the corresponding arene ruthenium dichloride dimers [(?6-arene)Ru(?2-Cl)Cl]2 (arene = C6H6, PriC6H4Me). While the reaction with triphenylphosphine and stannous chloride only gives the neutral mono(trichlorostannyl) complexes [(?6-C6H6)Ru(PPh3)(SnCl3)Cl] (1) and [(?6-PriC6H4Me)Ru(PPh3)(SnCl3)Cl] (2), the neutral di(trichlorostannyl) complex [(?6-PriC6H4Me)Ru(NCPh)(SnCl3)2] (3) could be obtained for the para-cymene deriv. with benzonitrile as addnl. ligand. By contrast, the analogous reaction with the benzene deriv. leads to a salt composed of the cationic mono(trichlorostannyl) complex [(?6-C6H6)Ru(NCPh)2(SnCl3)]+ (5) and of the anionic tris(trichlorostannyl) complex [(?6-C6H6)Ru(SnCl3)3]- (6). However, [(?6-PriC6H4Me)Ru(?2-Cl)Cl]2 reacts with SnCl2 and hexamethylenetetramine hydrochloride or 18-crown-6 to give the anionic di(trichlorostannyl) complex [(?6-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 Ã… (cationic complex). [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    Permanent Encapsulation or Host-Guest Behavior of Aromatic Molecules in Hexanuclear Arene Ruthenium Prisms
    Cationic arene Ru metallaprisms [Ru6(p-cymene)6(tpt)2(OO?OO)3]6+ {tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine; OO?OO = 9,10-dioxo-9,10-dihydroanthracene-1,4-diolato [1]6+, 6,11-dioxo-6,11-dihydronaphthacene-5,12-diolato [2]6+} were obtained from the corresponding dinuclear arene Ru complexes [Ru2(p-cymene)2(OO?OO)Cl2] by reaction with tpt and Ag trifluoromethanesulfonate. Arom. mols. (phenanthrene, pyrene, triphenylene, coronene) present during the synthesis of these metallaprisms are permanently encapsulated to give carceplex systems. All empty cages ([1]6+ and [2]6+) and carceplex systems ([guest?1]6+ and [guest?2]6+) were isolated in good yield as trifluoromethanesulfonate salts and characterized by NMR, UV, and IR spectroscopy. The host-guest properties of [1]6+ and [2]6+ were studied in soln. in the presence of small arom. mols. (phenanthrene and pyrene). The stability const. of assocn. (Ka) was estd. by NMR spectroscopy for the following host-guest systems: [phenanthrene?1]6+, [pyrene?1]6+ and [phenanthrene?2]6+, [pyrene?2]6+. All Ka values are larger than 2.0 × 104 M-1 for these host-guest systems ([D3]acetonitrile, 21°). [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    Designing the host-guest properties of tetranuclear arene ruthenium metalla-rectangles to accommodate a pyrene molecule
    (2010)
    Barry, Nicolas P. E.
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    Furrer, Julien
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    ; ;
    Cationic tetranuclear rectangular macrocyclic arene ruthenium complexes [Ru4(p-cymene)4(?-N-N)2(?-dhnq)2](CF3SO3)4 [1-3, dhnq = 5,8-dihydroxy-1,4-naphthoquinonato(2-); N-N = pyrazine, 4,4'-bipyridine, 1,2-bis(4-pyridyl)ethene], featuring Ru-dhnq-Ru-N-N-Ru-dhnq-Ru rectangle structures with adjustable Ru-Ru distances (7.0 Ã…, 11.2 Ã…, 13.6 Ã…, resp.), are obtained in methanol from the reaction of the dinuclear arene ruthenium precursor [Ru2(p-cymene)2(dhnq)2Cl2] with pyrazine or bipyridine linkers in the presence of AgCF3SO3. All complexes 1-3, isolated in good yield as triflate salts, have been characterized by NMR and IR spectroscopy. The interaction of these rectangular complexes with pyrene as a guest mol. has been studied in soln. by various NMR techniques (1D, DOSY, ROESY). In CD3CN, the pyrazine-contg. metalla-rectangle 1 shows no meaningful interactions with pyrene. On the other hand, the 4,4'-bipyridine- and 1,2-bis(4-pyridyl)ethylene-contg. metalla-rectangles 2 and 3 clearly interact with pyrene. DOSY measurements suggest that, in the case of the 4,4'-bipyridine complex 2, the interactions occur on the outside of the rectangular assembly, while in the case of dipyridylethylene complex 3 the pyrene mol. is found inside the hydrophobic cavity of the metalla-rectangle, thus giving rise to a host-guest system. [on SciFinder(R)]