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  • 1
    ISSN: 0044-2313
    Keywords: Hydridorhodium complexes ; reactions with CO and methanol ; synthesis of a carbonyl(methyl)rhodium(I) complex ; protonation reactions ; intramolecular rearrangement ; nitrosylrhodium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Dynamic Behaviour of [Rh2(μ-H)3H2(PiPr3)4]+. Contributions to the Reactivity of the Tetrahydridodirhodium Complex [Rh2H4(PiPr3)4]An improved synthesis of [Rh2H4(PiPr3)4] (2) from [Rh(η3-C3H5)(PiPr3)2] (1) or [Rh(η3-CH2C6H5)(PiPr3)2] (3) and H2 is described. Compound 2 reacts with CO or CH3OH to give trans-[RhH(CO)(PiPr3)2] (4) and with ethene/acetone to yield a mixture of 4 and trans-[RhCH3(CO)(PiPr3)2] (5). The carbonyl(methyl) complex 5 has also been prepared from trans-[RhCl(CO)(PiPr3)2] (6) and CH3MgI. Whereas the reaction of 2 with two parts of CF3CO2H leads to [RhH2(η2-O2CCF3) · (PiPr3)2] (8), treatment of 2 with one equivalent of CF3CO2H in presence of NH4PF6 gives the dinuclear compound [Rh2H5(PiPr3)4]PF6 (9a). The reactions of 2 with HBF4 and [NO]BF4 afford the complexes [Rh2H5(PiPr3)4]BF4 (9b) and trans-[RhF(NO)(PiPr3)2]BF4 (11), respectively. In solution, the cation [Rh2(μ-H)3H2(PiPr3)4]+ of the compounds 9a and 9b undergoes an intramolecular rearrangement in which the bridging hydrido and the phosphane ligands are involved.
    Notes: Es wird über eine verbesserte Synthese von [Rh2H4(PiPr3)4] (2) aus [Rh(η3-C3H5)(PiPr3)2] (1) oder [Rh(η3CH2C6H5)(PiPr3)2] (3) und H2 berichtet. Verbindung 2 reagiert mit CO oder CH3OH zu trans-[RhH(CO)(PiPr3)2] (4) und mit Ethen/Aceton zu einem Gemisch von 4 und trans-[RhCH3(CO) · (PiPr3)2] (5). Der Carbonyl(methyl)-Komplex 5 ist ebenfalls aus trans-[RhCl(CO)(PiPr3)2] (6) und CH3MgI erhältlich. Während die Reaktion von 2 mit zwei Teilen CF3CO2H zu [RhH2(η2O2CCF3)(PiPr3)2] (8) führt, entsteht aus 2 und einem Äquivalent CF3CO2H in Gegenwart von NH4PF6 die zweikernige Verbindung [Rh2H5(PiPr3)4]PF6 (9a). Die Umsetzungen von 2 mit HBF4 und [NO]BF4 liefern die Komplexsalze [Rh2H5(PiPr3)4]BF4 (9b) und trans-[RhF(NO)(PiPr3)2]BF4 (11). Das in den Verbindungen 9a und 9b vorliegende Kation [Rh2(μ-H)3H2(PiPr3)4]+ unterliegt in Lösung einer intramolekularen Umlagerung, in der die verbrückenden Hydridoliganden und die Phosphangruppen einbezogen sind.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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