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Herein, we demonstrate a ligand\u2010enabled proximity strategy in binuclear Cp*Ir(III) complexes, wherein the spatial confinement of two metal centers facilitates the concerted activation of multiple substrates. The optimized binuclear architecture, equipped with strategically positioned \u2012OH pendants, transforms the rate\u2010limiting termolecular collision into a kinetically favorable, low\u2010barrier pathway. This electronic and spatial cooperativity culminates in a turnover number of 1\u00a0540\u00a0000, placing the catalyst among the most efficient molecular systems reported for DMF production with selectivity approaching quantitative (&gt; 99%). Integrated computational and spectroscopic studies reveal that the dual\u2010Ir framework mitigates the entropic penalty inherent to termolecular processes, while the hydroxyl functionality polarizes the Ir\u2012H bond to promote H\n                    <jats:sub>2<\/jats:sub>\n                    heterolysis and CO\n                    <jats:sub>2<\/jats:sub>\n                    insertion. In situ NMR and infrared spectroscopy directly identify the key Ir\u2013hydride and Ir\u2013formate intermediates, providing experimental validation of the computationally predicted low\u2010barrier pathway. These findings establish for the first time how multimetallic cooperativity and secondary coordination sphere effects operate in concert to bypass the intrinsic kinetic limitations of single\u2010site catalysts.\n                  <\/jats:p>","DOI":"10.1002\/anie.7448862","type":"journal-article","created":{"date-parts":[[2026,7,26]],"date-time":"2026-07-26T17:53:20Z","timestamp":1785088400000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Proximal Ir\u2013Ir Cooperativity for Reprogramming the CO\n                    <sub>2<\/sub>\n                    \u2010to\u2010DMF Hydrogenation Pathway"],"prefix":"10.1002","volume":"65","author":[{"given":"Yuankang","family":"Xu","sequence":"first","affiliation":[{"name":"Shandong Key Laboratory of Intelligent Energy Materials School of Materials Science and Engineering China University of Petroleum (East China)  Qingdao People's Republic of 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