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Irradiation with UV light initialized in one case (<jats:bold>5\u2009a<\/jats:bold>, R=Dipp) the unselective formation of (<jats:sup>R<\/jats:sup>NHP\u2010H)MnH(CO)<jats:sub>4<\/jats:sub>] (<jats:bold>6\u2009a<\/jats:bold>) via cooperative addition of H<jats:sub>2<\/jats:sub> across the Mn=P double bond. In the other case (<jats:bold>5\u2009b<\/jats:bold>, R=Mes), addition of H<jats:sub>2<\/jats:sub> was unobservable and the reaction proceeded via decarbonylation to a dimeric species [(<jats:sup>R<\/jats:sup>NHP)<jats:sub>2<\/jats:sub>Mn<jats:sub>2<\/jats:sub>(CO)<jats:sub>7<\/jats:sub>] (<jats:bold>7\u2009b<\/jats:bold>) that was isolated and identified spectroscopically. Taking into account the outcome of further reaction studies under various conditions in the absence and presence of H<jats:sub>2<\/jats:sub>, both transformations can be explained in the context of a common mechanism involving decarbonylation to <jats:bold>7\u2009a<\/jats:bold>,<jats:bold>b<\/jats:bold> as the first step, and the different outcome is attributable to the fact that <jats:bold>7\u2009b<\/jats:bold> is unreactive towards both H<jats:sub>2<\/jats:sub> and CO while <jats:bold>7\u2009a<\/jats:bold> is not. DFT studies relate this divergence to deviations in the molecular constitution and stability arising from a different level of steric congestion. Preliminary studies suggest further that <jats:bold>5\u2009a<\/jats:bold>\/H<jats:sub>2<\/jats:sub> as well as <jats:bold>6\u2009a<\/jats:bold> enable the photo\u2010induced hydrogenation of styrene to ethyl benzene, even if the mechanism and possibly catalytic nature of this process remain yet unknown.<\/jats:p>","DOI":"10.1002\/chem.202302525","type":"journal-article","created":{"date-parts":[[2023,8,31]],"date-time":"2023-08-31T14:49:08Z","timestamp":1693493348000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Reversible Binding of Hydrogen and Styrene Coordination on a Manganese Phosphenium Complex"],"prefix":"10.1002","volume":"29","author":[{"given":"Marius","family":"Papendick","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie University of Stuttgart  Pfaffenwaldring 55 70550 Stuttgart Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9196-0466","authenticated-orcid":false,"given":"Dietrich","family":"Gudat","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie University of Stuttgart  Pfaffenwaldring 55 70550 Stuttgart Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2023,10,12]]},"reference":[{"key":"e_1_2_8_1_1","unstructured":"Selected reviews:"},{"key":"e_1_2_8_2_2","doi-asserted-by":"crossref","first-page":"2681","DOI":"10.1021\/acs.chemrev.8b00555","volume":"119","author":"Alig L.","year":"2019","journal-title":"Chem. 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