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  • 1
    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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  • 2
    ISSN: 0009-2940
    Keywords: Alkynes, (triphenylstannyl)- ; Rhodium(I) complexes, vinylidene ; Rhodium(III) complexes, alkynyl(hydrido)-and bis(alkynyl)hydrido- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of [RhCl(PiPr3)2]n (1) with stannylalkynes RC≡CSnPh3 [R = H, Me, Ph, CH2OH, CH2OMe, CMe2OH, CH(Me)OH, CH(Ph)OH, SiMe3, SnPh3] gives the vinylidenerhodium(I) complexes trans-[RhCl(=C=C(SnPh3)R)(PiPr3)2] (2a-j) in good to excellent yields. These compounds react with protic acids to give trans-[RhCl(=C=CHR)(PiPr3)2] and, for R = CH(Ph)OH, to give the allenylidene complex trans-[RhCl(=C=C=CHPh)-(PiPr3)2] (5). On treatment of 2b-j with PhHgCl, the heterodimetallic compounds [Rh(C≡C̊)(HgPh)Cl(PiPr3)2] (6a-i) are formed. The bis(alkynyl)rhodium(III) complexes [RhH(C≡CSi-Me3)(C≡CSnPh3)(py)(PiPr3)2] (9) and [Rh(C≡CSiMe3)(C≡C—CH2OMe)(SnPh3)(PiPr3)2] (10) are prepared from trans-[Rh-(C≡CSiMe3)(L)(PiPr3)2] (7, 8, L = py, C2H4) and HC≡CSnPh3 or Ph3SnC≡CCH2OMe, respectively. The crystal and molecular structures of trans-[RhCl(=C=C(SnPh3)CH2OMe)(PiPr3)2] (2e) and [Rh(C≡CCH2OMe)(HgPh)Cl(PiPr3)2] (6d) have been determined.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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