{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T09:44:12Z","timestamp":1791971052218,"version":"4.3.4"},"reference-count":102,"publisher":"Wiley","license":[{"start":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T00:00:00Z","timestamp":1791936000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T00:00:00Z","timestamp":1791936000000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100003246","name":"Nederlandse Organisatie voor Wetenschappelijk Onderzoek","doi-asserted-by":"publisher","award":["VI.Vidi.223.108"],"award-info":[{"award-number":["VI.Vidi.223.108"]}],"id":[{"id":"10.13039\/501100003246","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001721","name":"Rijksuniversiteit Groningen","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100001721","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"abstract":"ABSTRACT<\/jats:title>\n \n The bidentate ligands Ph\n 2<\/jats:sub>\n P(E)NHPPh\n 2<\/jats:sub>\n (E\u00a0=\u00a0 S, Se) feature phosphorous atoms in two different oxidation states and provide the potential to tune chemical reactivity through the choice of donor E. The mononuclear complexes [Ir(COD){\n \n \u03ba\n 2<\/jats:sup>\n \u2010P,E\u2010\n <\/jats:italic>\n Ph\n 2<\/jats:sub>\n P(E)NPPh\n 2<\/jats:sub>\n }]\u00a0(E\u00a0=\u00a0 S\n 1a<\/jats:bold>\n , Se\n 1b<\/jats:bold>\n ) were prepared from the dimer [IrClCOD]\n 2<\/jats:sub>\n (COD\u00a0=\u00a0 1,5\u2010cyclooctadiene) and the ligands Ph\n 2<\/jats:sub>\n P(E)NHPPh\n 2<\/jats:sub>\n (E\u00a0=\u00a0 S, Se) in the presence of KO\n t<\/jats:italic>\n Bu. Reaction of complexes\n 1a<\/jats:bold>\n and\n 1b<\/jats:bold>\n with CO afforded complexes [Ir(CO)\n 2<\/jats:sub>\n {\n \n \u03ba\n 2<\/jats:sup>\n \u2010P,E\u2010\n <\/jats:italic>\n Ph\n 2<\/jats:sub>\n P(E)NPPh\n 2<\/jats:sub>\n }] (E\u00a0=\u00a0 S\n 2a<\/jats:bold>\n , Se\n 2b<\/jats:bold>\n ). The carbonylation of\n 1a<\/jats:bold>\n was studied using UV\u2010vis absorption and Raman spectroscopies. A transient five\u2010coordinate intermediate [Ir(CO)(COD){\n \n \u03ba\n 2<\/jats:sup>\n <\/jats:italic>\n \u2010\n P,S\u2010<\/jats:italic>\n Ph\n 2<\/jats:sub>\n P(S)NPPh\n 2<\/jats:sub>\n }]\n 1a\u2010I<\/jats:bold>\n was observed. We support our findings with DFT calculations correlating the computed CO stretching frequencies with experimental values for this intermediate. The potential of complexes\n 1a<\/jats:bold>\n ,\n 1b<\/jats:bold>\n ,\n 2a<\/jats:bold>\n , and\n 2b<\/jats:bold>\n in the dehydrogenation of 2\u2010naphthylmethanol is explored, with dehydrogenation yielding 2\u2010naphthaldehyde and H\n 2<\/jats:sub>\n . This reactivity contrasts with the pathway reported earlier with other Ir catalysts, where additionally decarbonylation occurs. The yields with the COD derivatives,\n 1a<\/jats:bold>\n and\n 1b<\/jats:bold>\n , are moderate and higher than those of the carbonyl complexes,\n 2a<\/jats:bold>\n and\n 2b<\/jats:bold>\n . This difference highlights the effect of changing the ancillary ligands on the chemical behavior of the catalysts.\n <\/jats:p>","DOI":"10.1002\/chem.71656","type":"journal-article","created":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T08:44:16Z","timestamp":1791967456000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Ir Complexes With Mixed\u2010Valent Bidentate Ligands: From Complex Synthesis to Catalytic Application"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0009-0007-7125-0786","authenticated-orcid":false,"given":"C. 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