CO Dissociation Mechanism in Racemization of Alcohols by a Cyclopentadienyl Ruthenium Dicarbonyl Catalyst

13CO exchange studies of racemization catalyst (η5-Ph5C5)Ru(CO)2Cl and (η5-Ph5C5)Ru(CO)2(Ot-Bu) by 13C NMR spectroscopy are reported. CO exchange for the active catalyst form, (η5-Ph5C5)Ru(CO)2(Ot-Bu) is approximately 20 times faster than that for the precatalyst (η5-Ph5C5)Ru(CO)2Cl. An inhibition o...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2011-03, Vol.133 (9), p.2820-2823
Main Authors: Warner, Madeleine C, Verho, Oscar, Bäckvall, Jan-E
Format: Article
Language:English
Subjects:
Chemistry
Kemi
NATURAL SCIENCES
NATURVETENSKAP
Organic chemistry
Organisk kemi
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Summary:13CO exchange studies of racemization catalyst (η5-Ph5C5)Ru(CO)2Cl and (η5-Ph5C5)Ru(CO)2(Ot-Bu) by 13C NMR spectroscopy are reported. CO exchange for the active catalyst form, (η5-Ph5C5)Ru(CO)2(Ot-Bu) is approximately 20 times faster than that for the precatalyst (η5-Ph5C5)Ru(CO)2Cl. An inhibition on the rate of racemization of (S)-1-phenylethanol was observed on addition of CO. These results support the hypothesis that CO dissociation is a key step in the racemization of sec-alcohols by (η5-Ph5C5)Ru(CO)2Cl, as also predicted by DFT calculations.
ISSN:0002-7863
1520-5126
1520-5126
DOI:10.1021/ja1098066