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Mechanisms of the CO2 Insertion into (PCP) Palladium Allyl and Methyl sigma-Bonds. A Kinetic and Computational Study
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2010 (English)In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 29, no 16, 3521-3529 p.Article in journal (Refereed) Published
Abstract [en]

The reaction of the sigma-bonded (PCP)Pd-Me complex (PCP = 2,6-bis[(di-tert-butylphosphino)methyl]phenyl) with CO2 is first-order in palladium and first-order in CO, with a rate constant k(s) = 8.9 +/- 0.8 M-1 s(-1) at 353 K. Activation parameters are Delta H double dagger = 73 7 kJ/mol and Delta S double dagger = 118 +/- 19 J/K mol. Based on this and theoretical calculations we propose an S(E)2 mechanism where the coordinated methyl group attacks a completely noncoordinated carbon dioxide molecule in a bimolecular reaction. The PCPPd-crotyl complex was synthesized in an 65:35 E:Z mixture, and it was shown to react with CO, to give the complex PCPPd-O(CO)CH(CH3)CHCH2 as a single isomer, where the former gamma-carbon has been carboxylated. Theoretical calculations again suggest an S(E)2 mechanism with a noncoordinated carbon dioxide reacting with the terminal carbon on the allyl group, forming an eta(2)-bonded olefin complex as an intermediate. The rearrangement of this intermediate to the O-bonded product is concluded to be rate determining. The crystal structure of PCPPd-O(CO)C(CH3)(2)CHCH2 is reported and as well as the solubility of carbon dioxide in benzene-d(6) at different pressures and temperatures.

Place, publisher, year, edition, pages
2010. Vol. 29, no 16, 3521-3529 p.
National Category
Biochemistry and Molecular Biology
URN: urn:nbn:se:kth:diva-26871DOI: 10.1021/om100325vISI: 000280794400009ScopusID: 2-s2.0-77955700670OAI: diva2:373672
QC 20101201Available from: 2010-12-01 Created: 2010-11-29 Last updated: 2010-12-01Bibliographically approved

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Ahlquist, Mårten S. G.
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