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Photo-induced ligand substitution of Cr(CO)6 in 1-pentanol probed by time resolved X-ray absorption spectroscopy.
Mascarenhas, Eric J; Fondell, Mattis; Büchner, Robby; Eckert, Sebastian; Vaz da Cruz, Vinícius; Föhlisch, Alexander.
Afiliación
  • Mascarenhas EJ; Universität Potsdam, Institut für Physik und Astronomie, 14476 Potsdam, Germany. eric.mascarenhas@helmholtz-berlin.de.
  • Fondell M; Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Institute for Methods and Instrumentation for Synchrotron Radiation Research, 12489 Berlin, Germany.
  • Büchner R; Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Institute for Methods and Instrumentation for Synchrotron Radiation Research, 12489 Berlin, Germany.
  • Eckert S; Universität Potsdam, Institut für Physik und Astronomie, 14476 Potsdam, Germany. eric.mascarenhas@helmholtz-berlin.de.
  • Vaz da Cruz V; Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Institute for Methods and Instrumentation for Synchrotron Radiation Research, 12489 Berlin, Germany.
  • Föhlisch A; Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Institute for Methods and Instrumentation for Synchrotron Radiation Research, 12489 Berlin, Germany.
Phys Chem Chem Phys ; 24(30): 17979-17985, 2022 Aug 03.
Article en En | MEDLINE | ID: mdl-35737440
Cr(CO)6 was investigated by X-ray absorption spectroscopy. The spectral signature at the metal edge provides information about the back-bonding of the metal in this class of complexes. Among the processes it participates in is ligand substitution in which a carbonyl ligand is ejected through excitation to a metal to ligand charge transfer (MLCT) band. The unsaturated carbonyl Cr(CO)5 is stabilized by solution media in square pyramidal geometry and further reacts with the solvent. Multi-site-specific probing after photoexcitation was used to investigate the ligand substitution photoreaction process which is a common first step in catalytic processes involving metal carbonyls. The data were analysed with the aid of TD-DFT computations for different models of photoproducts and signatures for ligand rearrangement after substitution were found. The rearrangement was found to occur in about 790 ps in agreement with former studies of the photoreaction.

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Phys Chem Chem Phys Asunto de la revista: BIOFISICA / QUIMICA Año: 2022 Tipo del documento: Article País de afiliación: Alemania Pais de publicación: Reino Unido

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Phys Chem Chem Phys Asunto de la revista: BIOFISICA / QUIMICA Año: 2022 Tipo del documento: Article País de afiliación: Alemania Pais de publicación: Reino Unido