Synthese und dynamisches Verhalten von [Rh2(μ-H)3H2(PiPr3)4]+. Beiträge zur Reaktivität des Tetrahydridodirhodium-Komplexes [Rh2H4(PiPr3)4] |
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| Authors: | J Wolf O Nürnberg M Schfer H Werner |
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| Institution: | J. Wolf,O. Nürnberg,M. Schäfer,H. Werner |
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| Abstract: | 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. |
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| Keywords: | Hydridorhodium complexes reactions with CO and methanol synthesis of a carbonyl(methyl)rhodium(I) complex protonation reactions intramolecular rearrangement nitrosylrhodium complexes |
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