Photo-induced ligand substitution of Cr(CO)6 in 1-pentanol probed by time resolved X-ray absorption spectroscopy. Issue 30 (23rd June 2022)

• Record Type: Journal Article
• Authors: Mascarenhas, Eric J.; Fondell, Mattis; Büchner, Robby; Eckert, Sebastian; Vaz da Cruz, Vinícius; Föhlisch, Alexander
• Is Part Of: Physical chemistry chemical physics. Volume 24:Issue 30(2022)
• Page Start: 17979
• Page End: 17985
• Publication Date: 2022-06-23
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d1cp05834g
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : The photo-induced ligand substitution reaction of Cr(CO)6 in 1-pentanol was investigated using time-resolved X-ray absorption spectroscopy. The results point to ligand rearrangement after photoexcitation. Abstract : 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.