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Photochemical Formation and Electronic Structure of an Alkane σ-Complex from Time-Resolved Optical and X-ray Absorption Spectroscopy

Jay, Raphael M. (author)
Uppsala universitet,Kemisk och biomolekylär fysik
Coates, Michael R., 1994- (author)
Stockholms universitet,Fysikum
Zhao, Huan (author)
Center for Free-Electron Laser Science, Department of Physics, University of Hamburg, 22761 Hamburg, Germany
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Winghart, Marc-Oliver (author)
Max Born Institute for Nonlinear Optics and Short Pulse Spectroscopy, 12489 Berlin, Germany
Han, Peng (author)
Max Born Institute for Nonlinear Optics and Short Pulse Spectroscopy, 12489 Berlin, Germany
Wang, Ru-Pan (author)
Center for Free-Electron Laser Science, Department of Physics, University of Hamburg, 22761 Hamburg, Germany
Harich, Jessica (author)
Center for Free-Electron Laser Science, Department of Physics, University of Hamburg, 22761 Hamburg, Germany
Banerjee, Ambar, 1985- (author)
Uppsala universitet,Kemisk och biomolekylär fysik
Wikmark, Hampus (author)
Uppsala universitet,Kemisk och biomolekylär fysik
Fondell, Mattis (author)
Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany
Nibbering, Erik T. J. (author)
Max Born Institute for Nonlinear Optics and Short Pulse Spectroscopy, 12489 Berlin, Germany
Odelius, Michael, 1966- (author)
Stockholms universitet,Fysikum
Huse, Nils (author)
Center for Free-Electron Laser Science, Department of Physics, University of Hamburg, 22761 Hamburg, Germany
Wernet, Philippe, 1971- (author)
Uppsala universitet,Kemisk och biomolekylär fysik
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 (creator_code:org_t)
American Chemical Society (ACS), 2024
2024
English.
In: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 146:20, s. 14000-14011
  • Journal article (peer-reviewed)
Abstract Subject headings
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  • C–H bond activation reactions with transition metals typically proceed via the formation of alkane σ-complexes, where an alkane C–H σ-bond binds to the metal. Due to the weak nature of metal–alkane bonds, σ-complexes are challenging to characterize experimentally. Here, we establish the complete pathways of photochemical formation of the model σ-complex Cr(CO)5-alkane from Cr(CO)6 in octane solution and characterize the nature of its metal–ligand bonding interactions. Using femtosecond optical absorption spectroscopy, we find photoinduced CO dissociation from Cr(CO)6 to occur within the 100 fs time resolution of the experiment. Rapid geminate recombination by a fraction of molecules is found to occur with a time constant of 150 fs. The formation of bare Cr(CO)5 in its singlet ground state is followed by complexation of an octane molecule from solution with a time constant of 8.2 ps. Picosecond X-ray absorption spectroscopy at the Cr L-edge and O K-edge provides unique information on the electronic structure of the Cr(CO)5-alkane σ-complex from both the metal and ligand perspectives. Based on clear experimental observables, we find substantial destabilization of the lowest unoccupied molecular orbital upon coordination of the C–H bond to the undercoordinated Cr center in the Cr(CO)5-alkane σ-complex, and we define this as a general, orbital-based descriptor of the metal–alkane bond. Our study demonstrates the value of combining optical and X-ray spectroscopic methods as complementary tools to study the stability and reactivity of alkane σ-complexes in their role as the decisive intermediates in C–H bond activation reactions.

Subject headings

NATURVETENSKAP  -- Kemi -- Fysikalisk kemi (hsv//swe)
NATURAL SCIENCES  -- Chemical Sciences -- Physical Chemistry (hsv//eng)

Keyword

Physical Chemistry
Fysikalisk kemi

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