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Accessing metal-spe...
Accessing metal-specific orbital interactions in C–H activation with resonant inelastic X-ray scattering
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- Banerjee, Ambar, 1985- (author)
- Uppsala universitet,Kemisk och biomolekylär fysik
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- Jay, Raphael (author)
- Uppsala universitet,Kemisk och biomolekylär fysik
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- Leitner, Torsten, 1979- (author)
- Uppsala universitet,Institutionen för fysik och astronomi
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- Wang, Ru-Pan (author)
- Center for Free-Electron Laser Science, Department of Physics, University of Hamburg, 22761 Hamburg, Germany
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- Harich, Jessica (author)
- Center for Free-Electron Laser Science, Department of Physics, University of Hamburg, 22761 Hamburg, Germany
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- Stefanuik, Robert (author)
- Uppsala universitet,Kemisk och biomolekylär fysik
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- Coates, Michael R., 1994- (author)
- Stockholms universitet,Fysikum,Department of Physics, Stockholm University, AlbaNova University Center, 106 91 Stockholm, Sweden
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- Beale, Emma V. (author)
- Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland
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- Kabanova, Victoria (author)
- Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland
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- Kahraman, Abdullah (author)
- Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland
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- Wach, Anna (author)
- Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland;Institute of Nuclear Physics, Polish Academy of Sciences, PL-31342 Krakow, Poland
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- Ozerov, Dmitry (author)
- Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland
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- Arrell, Christopher (author)
- Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland
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- Milne, Christopher (author)
- European XFEL GmbH, 22869 Schenefeld, Germany
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- Johnson, Philip J. M. (author)
- Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland
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- Cirelli, Claudio (author)
- Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland
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- Bacellar, Camila (author)
- Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland
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- Huse, Nils (author)
- Center for Free-Electron Laser Science, Department of Physics, University of Hamburg, 22761 Hamburg, Germany
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- Odelius, Michael, 1966- (author)
- Stockholms universitet,Fysikum,Department of Physics, Stockholm University, AlbaNova University Center, 106 91 Stockholm, Sweden
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- Wernet, Philippe, 1971- (author)
- Uppsala universitet,Kemisk och biomolekylär fysik
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(creator_code:org_t)
- Royal Society of Chemistry, 2024
- 2024
- English.
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In: Chemical Science. - : Royal Society of Chemistry. - 2041-6520 .- 2041-6539. ; 15:7, s. 2398-2409
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Abstract
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- Photochemically prepared transition-metal complexes are known to be effective at cleaving the strong C–H bonds of organic molecules in room temperature solutions. There is also ample theoretical evidence that the two-way, metal to ligand (MLCT) and ligand to metal (LMCT), charge-transfer between an incoming alkane C–H group and the transition metal is the decisive interaction in the C–H activation reaction. What is missing, however, are experimental methods to directly probe these interactions in order to reveal what determines reactivity of intermediates and the rate of the reaction. Here, using quantum chemical simulations we predict and propose future time-resolved valence-to-core resonant inelastic X-ray scattering (VtC-RIXS) experiments at the transition metal L-edge as a method to provide a full account of the evolution of metal–alkane interactions during transition-metal mediated C–H activation reactions. For the model system cyclopentadienyl rhodium dicarbonyl (CpRh(CO)2), we demonstrate, by simulating the VtC-RIXS signatures of key intermediates in the C–H activation pathway, how the Rh-centered valence-excited states accessible through VtC-RIXS directly reflect changes in donation and back-donation between the alkane C–H group and the transition metal as the reaction proceeds via those intermediates. We benchmark and validate our quantum chemical simulations against experimental steady-state measurements of CpRh(CO)2 and Rh(acac)(CO)2 (where acac is acetylacetonate). Our study constitutes the first step towards establishing VtC-RIXS as a new experimental observable for probing reactivity of C–H activation reactions. More generally, the study further motivates the use of time-resolved VtC-RIXS to follow the valence electronic structure evolution along photochemical, photoinitiated and photocatalytic reactions with transition metal complexes.
Subject headings
- NATURVETENSKAP -- Kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences (hsv//eng)
- NATURVETENSKAP -- Kemi -- Teoretisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)
- NATURVETENSKAP -- Kemi -- Oorganisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)
- NATURVETENSKAP -- Kemi -- Fysikalisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Physical Chemistry (hsv//eng)
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Banerjee, Ambar, ...
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Jay, Raphael
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Leitner, Torsten ...
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Wang, Ru-Pan
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Harich, Jessica
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Stefanuik, Rober ...
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Coates, Michael ...
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Beale, Emma V.
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Kabanova, Victor ...
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Kahraman, Abdull ...
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Wach, Anna
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Ozerov, Dmitry
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Arrell, Christop ...
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Milne, Christoph ...
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Johnson, Philip ...
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Cirelli, Claudio
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Bacellar, Camila
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Huse, Nils
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Odelius, Michael ...
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Wernet, Philippe ...
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- About the subject
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- NATURAL SCIENCES
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NATURAL SCIENCES
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and Chemical Science ...
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- NATURAL SCIENCES
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NATURAL SCIENCES
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and Chemical Science ...
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and Theoretical Chem ...
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- NATURAL SCIENCES
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NATURAL SCIENCES
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and Chemical Science ...
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and Inorganic Chemis ...
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- NATURAL SCIENCES
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NATURAL SCIENCES
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and Chemical Science ...
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and Physical Chemist ...
- Articles in the publication
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Chemical Science
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Uppsala University
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Stockholm University