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In Situ Structural Determination of a Homogeneous Ruthenium Racemization Catalyst and Its Activated Intermediates Using X-Ray Absorption Spectroscopy
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, Stockholm, Sweden; Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University, Stockholm, Sweden; Borregaard, Sarpsborg, Norway.
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, Stockholm, Sweden.
Department of Molecular Sciences, Swedish University of Agricultural Sciences, Uppsala, Sweden; Wigner Research Centre for Physics, Konkoly-Thege Miklós út 29–33, Budapest, Hungary.
Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University, Stockholm, Sweden; Department of Molecular Sciences, Swedish University of Agricultural Sciences, Uppsala, Sweden.
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2020 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 26, p. 3411-3419Article in journal (Refereed) Published
Abstract [en]

The activation process of a known Ru‐catalyst, dicarbonyl(pentaphenylcyclopentadienyl)ruthenium chloride, has been studied in detail using time resolved in situ X‐ray absorption spectroscopy. The data provide bond lengths of the species involved in the process as well as information about bond formation and bond breaking. On addition of potassium tert‐butoxide, the catalyst is activated and an alkoxide complex is formed. The catalyst activation proceeds via a key acyl intermediate, which gives rise to a complete structural change in the coordination environment around the Ru atom. The rate of activation for the different catalysts was found to be highly dependent on the electronic properties of the cyclopentadienyl ligand. During catalytic racemization of 1‐phenylethanol a fast‐dynamic equilibrium was observed.

Place, publisher, year, edition, pages
John Wiley & Sons, 2020. Vol. 26, p. 3411-3419
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Natural Sciences
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URN: urn:nbn:se:miun:diva-40669DOI: 10.1002/chem.201905479ISI: 000515398900001Scopus ID: 2-s2.0-85081759341OAI: oai:DiVA.org:miun-40669DiVA, id: diva2:1506865
Available from: 2020-12-04 Created: 2020-12-04 Last updated: 2021-05-04Bibliographically approved

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Bäckvall, Jan-Erling

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