Issue 39, 2019

Photochemical or electrochemical bond breaking – exploring the chemistry of (μ2-alkyne)Co2(CO)6 complexes using time-resolved infrared spectroscopy, spectro-electrochemical and density functional methods

Abstract

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.

Graphical abstract: Photochemical or electrochemical bond breaking – exploring the chemistry of (μ2-alkyne)Co2(CO)6 complexes using time-resolved infrared spectroscopy, spectro-electrochemical and density functional methods

Supplementary files

Article information

Article type
Paper
Submitted
22 Jul 2019
Accepted
02 Sep 2019
First published
02 Sep 2019

Dalton Trans., 2019,48, 14642-14652

Photochemical or electrochemical bond breaking – exploring the chemistry of (μ2-alkyne)Co2(CO)6 complexes using time-resolved infrared spectroscopy, spectro-electrochemical and density functional methods

J. C. Manton, F. J. R. Cerpentier, E. C. Harvey, I. P. Clark, G. M. Greetham, C. Long and M. T. Pryce, Dalton Trans., 2019, 48, 14642 DOI: 10.1039/C9DT03006A

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