{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,30]],"date-time":"2026-10-30T16:12:55Z","timestamp":1793376775174,"version":"4.5.0"},"reference-count":72,"publisher":"Wiley","issue":"56","license":[{"start":{"date-parts":[[2026,8,21]],"date-time":"2026-08-21T00:00:00Z","timestamp":1787270400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,8,21]],"date-time":"2026-08-21T00:00:00Z","timestamp":1787270400000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Small"],"published-print":{"date-parts":[[2026,10]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    Homogeneous systems, while highly active, are inherently fragile and prone to catalyst deactivation through metal aggregation, ligand dissociation, and irreversible formation of catalytically inactive palladium black, thereby limiting recyclability during cross\u2010coupling. In contrast, supported heterogeneous catalysts often sacrifice reactivity due to restricted site accessibility, perturbed electronic environments, and uncontrolled metal leaching. Overcoming this dichotomy requires control over palladium speciation under turnover conditions, an objective that remains unmet for C\u2500N cross\u2010coupling. Herein, we report a heterogeneous palladium catalyst embedded in micro\u2010confined spaces to resolve this long\u2010standing limitation and establish a new paradigm for C\u2500N cross\u2010coupling. A hydrophobic confined environment provided by a hyper\u2010crosslinked polymer integrated with\n                    <jats:italic>t<\/jats:italic>\n                    \u2010BuXPhos, and the system selectively stabilises catalytically competent low\u2010valent Pd while suppressing aggregation, ligand dissociation, and metal leaching. Interestingly, this confinement preserves substrate accessibility via dynamic exchange at the material\u2010water interface with the synergy of a non\u2010ionic surfactant CNSL\u20101000\u2010M, enabling C\u2500N coupling at parts\u2010per\u2010million (ppm) palladium loadings. Our catalyst operating at \u2264500\u00a0ppm exhibits initial rates up to 31\u2010fold higher than its homogeneous analogue. We have demonstrated the recyclability over five successive cycles, affording a cumulative turnover number (TON) of 2.2 \u00d7 10\n                    <jats:sup>4<\/jats:sup>\n                    , the highest value reported to date for heterogeneous C\u2500N cross\u2010coupling.\n                  <\/jats:p>","DOI":"10.1002\/smll.74969","type":"journal-article","created":{"date-parts":[[2026,8,21]],"date-time":"2026-08-21T11:12:37Z","timestamp":1787310757000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Bridging the Gap: Heterogeneous Micro\u2010Confined Palladium Catalysts Surpassing Homogeneous Systems for C\u2013N Cross\u2010Coupling in Water"],"prefix":"10.1002","volume":"22","author":[{"given":"Rajan","family":"Yadav","sequence":"first","affiliation":[{"name":"Department of Inorganic and Physical Chemistry Indian Institute of Science  Bangalore 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