{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T00:56:33Z","timestamp":1760316993081,"version":"build-2065373602"},"reference-count":27,"publisher":"Wiley","issue":"63","license":[{"start":{"date-parts":[[2024,10,29]],"date-time":"2024-10-29T00:00:00Z","timestamp":1730160000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100001691","name":"Japan Society for the Promotion of Science","doi-asserted-by":"publisher","award":["JP21K14647"],"award-info":[{"award-number":["JP21K14647"]}],"id":[{"id":"10.13039\/501100001691","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2024,11,12]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>We present the photoreaction of newly prepared bis(6,6\u2019\u2010dimethyl\u20102,2\u2019\u2010bipyridine)(oxalato)rhodium(III) ([Rh(N\u2009N)<jats:sub>2<\/jats:sub>(ox)]<jats:sup>+<\/jats:sup>) in CD<jats:sub>3<\/jats:sub>OD. Photoirradiation of this complex causes the dissociation of ox, followed by the formation of the unprecedented Rh(III) complex with Rh\u2212H and Rh\u2212C \u03c3 bonds, [Rh(N\u2009N)(C\u2009N)(H)(CD<jats:sub>3<\/jats:sub>OD)]<jats:sup>+<\/jats:sup> (C\u2009N=[6,6\u2019\u2010dimethyl\u20102,2\u2019\u2010bipyridine]\u20103\u2010yl\u2010\u03ba<jats:italic>C<\/jats:italic><jats:sup>3<\/jats:sup>,\u03ba<jats:italic>N<\/jats:italic><jats:sup>1\u2019<\/jats:sup>). This hydride formation and cyclometallation spontaneously proceed owing to the conflict between the steric hindrance arising from the methyl groups of N\u2009N and the driving force for the structural change due to [Rh(N\u2009N)<jats:sub>2<\/jats:sub>]<jats:sup>+<\/jats:sup> formation. Although [Rh(N\u2009N)(C\u2009N)(H)(CD<jats:sub>3<\/jats:sub>OD)]<jats:sup>+<\/jats:sup> is initially converted to [Rh(N\u2009N)<jats:sub>2<\/jats:sub>]<jats:sup>+<\/jats:sup> by photoirradiation, it is immediately regenerated by the rollover cyclometallation of the [Rh(N\u2009N)<jats:sub>2<\/jats:sub>]<jats:sup>+<\/jats:sup> complex. [Rh(N\u2009N)(C\u2009N)(H)(CD<jats:sub>3<\/jats:sub>OD)]<jats:sup>+<\/jats:sup> undergoes H\/D exchange for the H atoms in the Rh\u2212H bond and at the 3, 3\u2019\u2010positions of the N\u2009N ligand during the photoirradiation. DFT calculations predict with reasonable certainty the spontaneous structural change of [Rh(N\u2009N)<jats:sub>2<\/jats:sub>]<jats:sup>+<\/jats:sup> to [Rh(N\u2009N)(C\u2009N)(H)(CD<jats:sub>3<\/jats:sub>OD)]<jats:sup>+<\/jats:sup> and the subsequent photodriven Rh\u2212C bond rupture leading to the formation of [Rh(N\u2009N)<jats:sub>2<\/jats:sub>]<jats:sup>+<\/jats:sup> accompanied by H\/D exchange reactions.<\/jats:p>","DOI":"10.1002\/chem.202402067","type":"journal-article","created":{"date-parts":[[2024,7,31]],"date-time":"2024-07-31T00:09:33Z","timestamp":1722384573000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Sequential H\/D Exchanges Resulting from Rollover\u2010Cyclometallation during Photoirradiation of Rhodium(III) Complex in Methanol\u2010d<sub>4<\/sub>"],"prefix":"10.1002","volume":"30","author":[{"given":"Shota","family":"Tanaka","sequence":"first","affiliation":[{"name":"Department of Materials Sciences Graduate School of Nanobioscience Yokohama City University  22-2 Seto, Kanazawa-ku Yokohama 236-0027 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9385-961X","authenticated-orcid":false,"given":"Shingo","family":"Hattori","sequence":"additional","affiliation":[{"name":"Department of Materials Sciences Graduate School of Nanobioscience Yokohama City University  22-2 Seto, Kanazawa-ku Yokohama 236-0027 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7571-9210","authenticated-orcid":false,"given":"Kazuteru","family":"Shinozaki","sequence":"additional","affiliation":[{"name":"Department of Materials Sciences Graduate School of Nanobioscience Yokohama City University  22-2 Seto, Kanazawa-ku Yokohama 236-0027 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,10,29]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/C1SC00651G"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr900279a"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00334a031"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100466a025"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00506a002"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic50224a079"},{"key":"e_1_2_7_7_1","doi-asserted-by":"crossref","unstructured":"W.\u2005A. 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