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  • 1
    ISSN: 0009-2940
    Keywords: Ruthenium complexes ; Osmium complexes ; Insertion reactions ; Carbon disulfide ; Carbon dioxide ; Methyl isothiocyanate ; Zwitterionic ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The five-coordinate chloro(hydrido)- and hydrido(iodo)ruthenium(II) and -osmium(II) compounds [MHX(CO)(PiPr3)2] (1, 2, 6, 7) react with CS2 to give the octahedral dithioformato complexes [MCl(CO)(PiPr3)2(η2-S2CH)] (3, 4, 8, 9) in excellent yields. In the initial step, an addition of the heteroallene to the metal center occurs which is followed by insertion of CS2 into the M - H bond. On treatment of the dichlororuthenium(II) derivative [RuCl2(CO)(PiPr3)2] (10), which is prepared from RuCl3 · aq and PiPr3 in methanol, with carbon disulfide insertion into one of the Ru - PiPr3 bonds takes place to give the six-coordinate ruthenium(II) complex 12 with zwitterion -S2CPiPr3+ as a chelating ligand. While the reaction of [OsH(SPh)(CO)(PiPr3)2] (13) with MeSCN leads to addition of the thionitrile to the metal center, the starting material reacts with MeNCS by insertion of the heteroallene into the Os - SPh bond to give two stereoisomers 15a, b, in which the nitrogen atom of the chelate ring is either cis or trans to the hydrido ligand. The octahedral methoxydithiocarbonato- and formatoosmium(II) compounds 16 and 17 are prepared from 2 and CS2 or CO2 in the presence of NaOMe. The crystal and molecular structures of 4 (M = Os), 12 and 15a have been determined.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0009-2940
    Keywords: Cationic amido osmium(II) complexes, synthesis from dichloro metal precursor and primary amines ; Os-N double bond ; Aldimino(hydrido)osmium(II) complex, formation by β1-hydride migration ; Amino(chloro)osmium(II) complex, preparation by protonation of an amido derivate ; Dinuclear imidoosmium complex, presence of a Os2N2 four-membered ring ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbene-Type Amidoosmium Complexes with an Os—N Double Bond: Synthesis, Structure and Reactivity of [(Mes)Os(=NHR)(PiPr3)]PF6*The reaction of [(Mes)Os(PiPr3)Cl2] (1) (Mes=1,3,5-C6H3Me3) with primary amines RNH2 (R=Ph, Me, Et) in acetone/water (1:1) gives, after addition of KPF6, the amidoosmium(II) complexes [(Mes)Os(=NHR)(PiPr3)]PF6 (2-4) in 60-80% yield. From 1 and Et2NH, the chloro(hydrido)compound [(Mes)1-OsH(PiPr3)Cl] (5) is formed. The X-ray structural analysis of 2 reveals that the geometry around the osmium atom is trigonalplanar (with the midpoint of the mesitylene ring as one coordination site) and that the Os—N distance of 1.923(4) Å is in agreement with an Os—N double bond. Thermolysis of 4 (R=Et) at 165°C leads to the formation of the aldimino(hydrido)osmium complex [(Mes)OsH(NH=CHMe)(PiPr3)]PF6 (6) by β1-hydride migration from the NCH2 carbon atom to the metal atom. Protonation of 3 (R=Me) with HCl gives the amine complex [(Mes)Os(NH2Me)(PiPr3)Cl]PF6 (7), whereas on treatment of 3 and 4 with CD3NO2 the deuterated derivatives [(Mes)Os(=NDR)(PiPr3)]PF6 ([D1]-3, [D1]-4) are almost quantitatively formed. Compound 2 (R=Ph) reacts with KOtBu by proton abstraction and phosphane elimination to give the dinuclear imidoosmium complex [(Mes)2Os2(μ1-NPh)2] (8).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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