Photochemical or electrochemical bond breaking - exploring the chemistry of (μ 2 -alkyne)Co 2 (CO) 6 complexes using time-resolved infrared spectroscopy, spectro-electrochemical and density functional methods

The photochemistry of (μ2-CRCR')Co2(CO)6 complexes (R = pyrenyl, R' = H; R = pyrenyl, R' = ferrocenyl; R = ferrocenyl, R = H) was investigated by ps-time-resolved infrared spectroscopy at room temperature in dichloromethane solution. The main focus of these studies was to determine th...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2019-10, Vol.48 (39), p.14642-14652
Main Authors: Manton, Jennifer C, Cerpentier, Florian J R, Harvey, Emma C, Clark, Ian P, Greetham, Gregory M, Long, Conor, Pryce, Mary T
Format: Article
Language:English
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Summary:The photochemistry of (μ2-CRCR')Co2(CO)6 complexes (R = pyrenyl, R' = H; R = pyrenyl, R' = ferrocenyl; R = ferrocenyl, R = H) was investigated by ps-time-resolved infrared spectroscopy at room temperature in dichloromethane solution. The main focus of these studies was to determine the primary photoprocess relevant to the light assisted Pauson-Khand reaction. These studies were supported by spectro-electrochemical investigations and density functional calculations which suggest that the primary process to initiate the Pauson-Khand reaction involves a homolytic cleavage of the Co-Co bond forming a high-spin diradical species and not CO-loss as previously thought.
ISSN:1477-9226
1477-9234
DOI:10.1039/c9dt03006a