Übergangsmetall–carben-komplexe : LXXIII. Kinetik und mechanismus der isomerisierung von cis- und trans-tetracarbonyl-methoxymethylcarben-phosphin-chrom(0)-komplexen

作者: Helmut Fischer , Ernst Otto Fischer , Helmut Werner

DOI: 10.1016/S0022-328X(00)83832-2

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摘要: Abstract The kinetics of the isomerisation reactions tetracarbonyl(methoxymethylcarbene)(trialkylphosphine)chromium(0), (CO)4Cr[C(OCH3)CH3] [PR3] (R = C2H5, C6H11), according to equation: have been studied in methylcyclohexane and toluene. interconversion geometrical isomers follows a first-order rate law: d[(II)]/dt k1[(II)]. Excess free phosphine or carbon monoxide has no significant influence on reaction. Phosphine exchange experiments also show that takes place via neither nor C cleavage. results are discussed basis an intramolecular mechanism, which plausibly explains very small values activation entropies.

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