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    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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