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Spectroscopic studies suggest that the anellation enhances the \u03c0\u2010acceptor ability of the NHP\u2010units, which is confirmed by the facile electrochemical reduction of the complex to a spectroscopically characterized radical anion. Co\u2010photolysis with H<jats:sub>2<\/jats:sub> allowed extensive conversion into a \u03c3\u2010H<jats:sub>2<\/jats:sub>\u2010complex, which shows a diverse reactivity towards donors and isomerizes under H\u2212H bond fission and shift of a hydride to a P\u2010ligand. The product carrying phosphenium, phosphine and hydride ligands was also synthesized independently and reacts reversibly with CO and MeCN to yield bis\u2010phosphine complexes under concomitant Cr\u2010to\u2010P\u2010shift of a hydride. In contrast, CO<jats:sub>2<\/jats:sub> was not only bound but reduced to give an isolable formato complex, which reacted with ammonia borane under partial recovery of the metal hydride and production of formate. Further elaboration of the reactions of the chromium complexes with CO<jats:sub>2<\/jats:sub> and NH<jats:sub>3<\/jats:sub>BH<jats:sub>3<\/jats:sub> allowed to demonstrate the feasibility of a Cr\u2010catalyzed transfer hydrogenation of CO<jats:sub>2<\/jats:sub> to methanol. The various complexes described were characterized spectroscopically and in several cases by XRD studies. Further insights in reactivity patterns were provided through (spectro)electrochemical studies and DFT calculations.<\/jats:p>","DOI":"10.1002\/chem.202401714","type":"journal-article","created":{"date-parts":[[2024,6,11]],"date-time":"2024-06-11T15:06:39Z","timestamp":1718118399000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Chromium Complexes with Benzanellated N\u2010Heterocyclic Phosphenium Ligands\u2013Synthesis, Reactivity and Application in Catalytic CO<sub>2<\/sub> Reduction"],"prefix":"10.1002","volume":"30","author":[{"given":"Nicholas","family":"Birchall","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie University of Stuttgart  Pfaffenwaldring 55 70550 Stuttgart Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Fridolin","family":"Hennh\u00f6fer","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie University of 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