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Herein, we report that such a pathway can be realized over a sub\u2010nanostructured europium hydride (Eu\u2013H) catalyst under mild condition. The Eu\u2013H catalyst achieved a biphenyl production of 53.7\u00a0mmol\u00a0g\n                    <jats:sub>Eu<\/jats:sub>\n                    <jats:sup>\u22121<\/jats:sup>\n                    with a turnover number (TON) of 16.3 over 144\u00a0h at 150\u00a0\u00b0C. Mechanistic studies suggest that hydride species (H\n                    <jats:sup>\u2212<\/jats:sup>\n                    ) in Eu\u2013H preferentially deprotonate benzene to form a [C\n                    <jats:sub>6<\/jats:sub>\n                    H\n                    <jats:sub>5<\/jats:sub>\n                    \u2013Eu] intermediate, which subsequently undergoes nucleophilic attack on another benzene molecule, resulting in biphenyl formation and regeneration of the Eu\u2013H species to complete the catalytic cycle. This work not only provides a strategy for benzene coupling to biphenyl but also demonstrates the promising role of hydrides in transforming arenes into value\u2010added molecules.\n                  <\/jats:p>","DOI":"10.1002\/anie.202517421","type":"journal-article","created":{"date-parts":[[2025,10,18]],"date-time":"2025-10-18T16:03:42Z","timestamp":1760803422000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Catalytic Non\u2010Oxidative C\u2013C Coupling of Benzene to Biphenyl Over Sub\u2010Nanostructured Europium Hydride"],"prefix":"10.1002","volume":"64","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-7474-1416","authenticated-orcid":false,"given":"Yongli","family":"Cai","sequence":"first","affiliation":[{"name":"Dalian Institute of Chemical Physics Chinese Academy of Sciences  Dalian 116023 China"},{"name":"Center of Materials and Optoelectronics Engineering University of Chinese Academy of Sciences  Beijing 100049 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Shixiong","family":"Zhang","sequence":"additional","affiliation":[{"name":"Dalian Institute of Chemical Physics Chinese Academy of Sciences  Dalian 116023 China"},{"name":"Center of Materials and Optoelectronics Engineering University of Chinese Academy of Sciences  Beijing 100049 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yanbo","family":"Deng","sequence":"additional","affiliation":[{"name":"Dalian Institute of Chemical Physics Chinese Academy of Sciences  Dalian 116023 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Li","family":"Rao","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Green Pesticide College of Chemistry Central China Normal University  Wuhan 430079 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0229-8555","authenticated-orcid":false,"given":"Jianping","family":"Guo","sequence":"additional","affiliation":[{"name":"Dalian Institute of Chemical Physics Chinese Academy of Sciences  Dalian 116023 China"},{"name":"Center of Materials and Optoelectronics Engineering University of Chinese Academy of Sciences  Beijing 100049 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ping","family":"Chen","sequence":"additional","affiliation":[{"name":"Dalian Institute of Chemical Physics Chinese Academy of Sciences  Dalian 116023 China"},{"name":"Center of Materials and Optoelectronics Engineering University of Chinese Academy of Sciences  Beijing 100049 China"},{"name":"State Key Laboratory of Catalysis Dalian Institute of Chemical Physics Chinese Academy of Sciences  Dalian 116023 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