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  • 1
    ISSN: 0009-2940
    Keywords: Osmium complexes ; Hydrido complexes ; Functionalized phosphane ligands ; Phosphanylmethanide ligand ; Phosphanyl alcoholate ligand ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mononuclear dichloroosmium(II) complexes [(mes)-Os(L)Cl2] (2-5) with the phosphanyl ether L = iPr2PCH2-CH2OMe and phosphanyl esters L = IPr2P(CH2)nCO2R as ligands are obtained from [(mes)OsCl2]n and L in almost quantitative yield. While compound 3 (L = iPr2PCH2CH2CO2Me) reacts with Mg/Hg in THF in the presence of ethanol to give the monohydrido derivative 6, treatment of 4 (L = iPr2PCH2-CO2Me) or 5 (L = iPr2PCH2CO2Et) with Al2O3/NaH in THF yields the phosphanylmethanide complexes [(mes)-Os{k2(P,C)-iPr2PCHCO2R}Cl] (7, 8). In contrast to the reaction of 4 with Mg/Hg in THF/EtOH which yields the dihydrido compound [(mes)OsH2{k(P)-iPr2PCH2CO2Me}] (10), the corresponding reaction of 4 with excess PhMgBr does not lead to an OsPh2 species but instead gives the new chelate complex [(mes)OsPh{k2(P,O)-iPr2PCH2CPh2O}] (11). The crystal and molecular structures of 7 and 11 were determined.
    Additional Material: 2 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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