Mechanism of Dissociation

  • Author: ChemistryViews
  • Published: 15 February 2011
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA
  • Source / Publisher: Journal of the American Chemical Society/ACS Publications
thumbnail image: Mechanism of Dissociation

Ruthenium catalysts have a range of applications in racemizations and (transfer) hydrogenations. Understanding the mechanisms behind these reactions could lead to improved design and better catalysis.

Jan Bäckvall and co-workers, Stockholm University, Sweden, have studied the CO exchange that occurs with two Ru catalysts: (η5-Ph5C5)Ru(CO)2Cl and (η5-Ph5C5)Ru(CO)2(Ot-Bu). The catalysts were employed in the racemization of sec-alcohols, and inclusion of 13CO was monitored by 13C NMR. CO exchange was shown to be 20 times faster for the active tert-butoxide complex than the ruthenium chloride precursor complex.

Addition of CO was also shown to result in a reduction in the rate of (S)-1-phenylethanol racemization, supporting the idea that reversible CO dissociation is a key step in the racemization mechanism of sec-alcohols with these type of Ru catalysts.

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