Issue 30, 2022

Photo-induced ligand substitution of Cr(CO)6 in 1-pentanol probed by time resolved X-ray absorption spectroscopy

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.

Graphical abstract: Photo-induced ligand substitution of Cr(CO)6 in 1-pentanol probed by time resolved X-ray absorption spectroscopy

Supplementary files

Article information

Article type
Paper
Submitted
21 Dec 2021
Accepted
06 Jun 2022
First published
07 Jun 2022
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2022,24, 17979-17985

Photo-induced ligand substitution of Cr(CO)6 in 1-pentanol probed by time resolved X-ray absorption spectroscopy

E. J. Mascarenhas, M. Fondell, R. Büchner, S. Eckert, V. Vaz da Cruz and A. Föhlisch, Phys. Chem. Chem. Phys., 2022, 24, 17979 DOI: 10.1039/D1CP05834G

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