In Situ Structural Determination of a Homogeneous Ruthenium Racemization Catalyst and Its Activated Intermediates Using X-Ray Absorption Spectroscopy

Gustafson, Karl P. J.; Guðmundsson, Arnar; Bajnóczi, Éva G.; Yuan, Ning; Zou, Xiaodong; Persson, Ingmar; Bäckvall, Jan‐E.

doi:10.1002/chem.201905479

Title: In Situ Structural Determination of a Homogeneous Ruthenium Racemization Catalyst and Its Activated Intermediates Using X-Ray Absorption Spectroscopy

Journal Article · 23 January 2020 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.201905479 · OSTI ID:1623514

Gustafson, Karl P. J. ^[1]; Guðmundsson, Arnar ^[2]; Bajnóczi, Éva G. ^[3]; Yuan, Ning ^[4]; Zou, Xiaodong ^[2]; Persson, Ingmar ^[3];

^[2]

Stockholm Univ. (Sweden); DOE/OSTI
Stockholm Univ. (Sweden)
Swedish Univ. of Agricultural Sciences, Uppsala (Sweden)
Stockholm Univ. (Sweden); Swedish Univ. of Agricultural Sciences, Uppsala (Sweden)

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.

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Research Organization:: SLAC National Accelerator Laboratory, Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Sponsoring Organization:: Berzelii Center EXSELENT; Knut and Alice Wallenberg Foundation; National Institute of General Medical Sciences (NIGMS); National Institutes of Health (NIH); Swedish Research Council (VR); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1623514

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 15 Vol. 26; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chemistry
homogeneous catalysis
in situ EXAFS
racemization
ruthenium
spectroscopy

Title: In Situ Structural Determination of a Homogeneous Ruthenium Racemization Catalyst and Its Activated Intermediates Using X-Ray Absorption Spectroscopy

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References (51)

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