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Herein, we report the synthesis and reactivity of a well\u2010defined chromium\u2013aluminum hydride dinitrogen complex, [(depe)\n                    <jats:sub>2<\/jats:sub>\n                    (H)Cr(\n                    <jats:italic>\u03bc<\/jats:italic>\n                    \u2010N\n                    <jats:sub>2<\/jats:sub>\n                    )AlH\n                    <jats:sub>2<\/jats:sub>\n                    ]\n                    <jats:sub>2<\/jats:sub>\n                    (depe\u00a0=\u00a0Et\n                    <jats:sub>2<\/jats:sub>\n                    PCH\n                    <jats:sub>2<\/jats:sub>\n                    CH\n                    <jats:sub>2<\/jats:sub>\n                    PEt\n                    <jats:sub>2<\/jats:sub>\n                    ). Crystallographic and spectroscopic analyses reveal substantial N\n                    <jats:sub>2<\/jats:sub>\n                    reduction driven by a \u201cpush\u2013pull\u201d interaction between the electron\u2010rich Cr centers and the electrophilic Al Lewis acid core. Upon stoichiometric protonation with [Ph\n                    <jats:sub>2<\/jats:sub>\n                    NH\n                    <jats:sub>2<\/jats:sub>\n                    ]OTf, the highly activated bridging N\n                    <jats:sub>2<\/jats:sub>\n                    units undergo selective proton\u2010coupled reduction to release hydrazine (N\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    ) in up to 97% yield. Crucially, structure\u2013reactivity investigations reveal a clear correlation between the presence of the central Al\u2500H bonds and the selective hydrazine formation. Furthermore, the central aluminum hydrides exhibit high regioselectivity toward silyl electrophiles, enabling the precise construction of fully and partially substituted derivatives; notably, in\n                    <jats:bold>5\u20138<\/jats:bold>\n                    the Cr\u2500N\n                    <jats:sub>2\u2013<\/jats:sub>\n                    Al motif and terminal Cr\u2500H units are retained. Subsequent redox investigations demonstrate that deep chemical reduction induces a core rearrangement into a unique complex, [(depe)\n                    <jats:sub>2<\/jats:sub>\n                    (H)Cr(\n                    <jats:italic>\u03bc<\/jats:italic>\n                    \u2010N\n                    <jats:sub>2<\/jats:sub>\n                    )]\n                    <jats:sub>2<\/jats:sub>\n                    (\n                    <jats:italic>\u03bc<\/jats:italic>\n                    \u2010AlH\n                    <jats:sub>2<\/jats:sub>\n                    )(\n                    <jats:italic>\u03bc<\/jats:italic>\n                    \u2010Li), followed by multimetallic cleavage. These transformations underscore the essential role of the Lewis acidic Al(III) center in maintaining multimetallic structural integrity and sustaining N\n                    <jats:sub>2<\/jats:sub>\n                    activation. Overall, these findings define a heterobimetallic Cr\u2500Al hydride framework in which the central Al\u2500H motif governs stoichiometric hydrazine release and site\u2010selective hydride functionalization.\n                  <\/jats:p>","DOI":"10.1002\/anie.3346028","type":"journal-article","created":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T03:45:07Z","timestamp":1790653507000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Stoichiometric Reduction of Dinitrogen to Hydrazine Upon Protonation of Heterobimetallic Chromium\u2013Aluminum Hydride Complexes"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0009-0005-8663-3339","authenticated-orcid":false,"given":"Xuan\u2010Xuan","family":"Zhao","sequence":"first","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences (BNLMS) Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education College of Chemistry Peking University  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2200-3598","authenticated-orcid":false,"given":"Zhu\u2010Bao","family":"Yin","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences (BNLMS) Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education College of Chemistry Peking University  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Biguo","family":"Liang","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences (BNLMS) Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education College of Chemistry Peking University  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1124-5380","authenticated-orcid":false,"given":"Zhenfeng","family":"Xi","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences (BNLMS) Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education College of Chemistry Peking University  Beijing China"},{"name":"State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9733-803X","authenticated-orcid":false,"given":"Junnian","family":"Wei","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences (BNLMS) Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education College of Chemistry Peking University  Beijing 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