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FTIR spectroscopy, combined with density functional theory calculations, revealed a clean photo\u2010induced reaction in organic solvents (acetonitrile, pyridine, valeronitrile) to give mainly one photoproduct with monosubstitution of a carbonyl ligand for a solvent molecule. The highest photodissociation quantum yields were reached for the Cr<jats:sup>0<\/jats:sup> complex under UV irradiation (266\u2005nm). Based on previous investigations, the kinetics of the dark reverse reactions have now been determined, with reaction times of up to several hours in pyridine. Photochemical studies in the solid state (KBr matrix, frozen solution) also showed light\u2010induced reactivity with stabilization of the metastable intermediate with a free coordination site at very low temperature. The identified reactive species emphasizes a mechanism without ligand\u2013sphere reorganization.<\/jats:p>","DOI":"10.1002\/chem.202201038","type":"journal-article","created":{"date-parts":[[2022,6,15]],"date-time":"2022-06-15T22:09:30Z","timestamp":1655330970000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Mechanistic and Kinetic Investigations of ON\/OFF (Photo)Switchable Binding of Carbon Monoxide by Chromium(0), Molybdenum(0) and Tungsten(0) Carbonyl Complexes with a Pyridyl\u2010Mesoionic Carbene Ligand"],"prefix":"10.1002","volume":"28","author":[{"given":"Pit J.","family":"Boden","sequence":"first","affiliation":[{"name":"Department of Chemistry and State Research Center Optimas TU Kaiserslautern  Erwin-Schr\u00f6dinger-Stra\u00dfe 52 67663 Kaiserslautern Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Patrick","family":"Di 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