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  • 1
    ISSN: 0009-2940
    Keywords: Arsane, triisopropyl, rhodium complexes of ; Stibane, triisopropyl, rhodium complexes of ; Rhodium(I) complexes, square-planar, with carbonyl, ethylene, alkyne, and vinylidene ; Rhodium(III) compounds [RhH2Cl(EiPr3)2] (E=As, Sb), five-coordinate, dihydrido- ; Allenerhodium complexes, generation from alkynes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of the dimeric bis(olefin)rhodium(I) compounds [RhCl(olefin)2]2 [olefin=C8H14 (2), C2H4 (5)] with AsiPr3 and SbiPr3 gives mono- and dinuclear olefin(arsane) and olefin(stibane) complexes [RhCl(olefin)(EiPr3)]2 [olefin=C8H14 (3, 4), C2H4 (6, 7)] and trans-[RhCl(C2H4)(EiPr3)2] (8, 9). Treatment of 8 and 9 with CO, H2, and CPh2N2 leads to the displacement of the ethylene ligand with formation of the corresponding carbonyl (10, 11), dihydrido (12, 13), and diazoalkane (14) rhodium derivatives. In solution, compound 14 loses CPh2 to give trans-[RhCl(N2)(AsiPr3)2] (15). The alkyne complexes trans-[RhCl(HC≡C̊)(AsiPr3)2] (16-18), which are prepared either from 8 or [RhH2Cl(AsiPr3)2] (12) and HC≡C̊ (R=H, Ph, CO2Me), rearrange in solution to produce the vinylidenerhodium isomers trans-[RhCl(=C=CHR)(AsiPr3)2] (19-21). Reaction of 8 with HC≡CMe and HC≡CtBu leads directly to the vinylidene complexes 22, 23. Compound 8 reacts with excess propyne, but-2-yne, or 2,2-dimethylpent-2-yne to give the rhodium allenes trans-[RhCl(η2-CH2=C=CHR)(AsiPr3)2] (25-27) in nearly quantitative yields. With DC≡CMe as a substrate, it is shown that two propyne molecules are involved in the rearrangement to generate the coordinated allene. The crystal and molecular structure of trans-[RhCl(η2-CH2=C=CH2)(AsiPr3)2] (27) has been determined.
    Additional Material: 1 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.
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  • 3
    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.
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