{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T13:00:17Z","timestamp":1790600417123,"version":"4.1.0"},"reference-count":25,"publisher":"American Chemical Society (ACS)","issue":"9","license":[{"start":{"date-parts":[[2026,7,31]],"date-time":"2026-07-31T00:00:00Z","timestamp":1785456000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000165","name":"Division of Chemistry","doi-asserted-by":"publisher","award":["CHE 2345856"],"award-info":[{"award-number":["CHE 2345856"]}],"id":[{"id":"10.13039\/100000165","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000057","name":"National Institute of General Medical Sciences","doi-asserted-by":"publisher","award":["1R35GM159617-01"],"award-info":[{"award-number":["1R35GM159617-01"]}],"id":[{"id":"10.13039\/100000057","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,9,28]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Palladium-catalyzed cross-couplings are frequently limited by off-cycle deactivation pathways, particularly phosphine deligation followed by aggregation of Pd(0) to catalytically inactive palladium black. We report an \u201con-cycle enforcement\u201d strategy that employs a cooperative, nonalloyed trimetallic assembly\u2500Pd(0), Cu(I), and Mn(III)\u2500confined within PS-750-M\/HPMC micelles in water. In this architecture, Pd mediates the canonical oxidative addition and reductive elimination steps, Cu(I) accelerates transmetalation via a Cu-nucleophile intermediate, and Mn(II\/III) serves as a redox buffer that likely continuously reoxidizes off-cycle Pd(0) to micelle-soluble Pd(II), followed by its religation and reduction, thereby preventing Pd black formation. Spectroscopic analysis\u2500transmission electron microscopy, scanning transmission electron microscopy\u2013high-angle annular dark-field imaging, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy\u2500reveals that the three metals remain spatially separated in the assembly yet electronically complementary within a phosphorus-rich matrix, enabling persistent catalytic activity. The resulting platform supports rapid, selective C\u2013C couplings at 45 \u00b0C with broad substrate compatibility, including heteroarenes and terminal olefin\u2500containing partners, without olefin interference. The catalyst displays exceptional longevity, minimal metal leaching (&amp;lt;1 ppm), and robust scalability, with multicycle reactions and gram-scale processes proceeding efficiently even after extended catalyst storage. These findings establish redox-buffered, compartmentalized trimetallic assemblies as a general solution to enforcing on-cycle Pd catalysis in water.<\/jats:p>","DOI":"10.1021\/jacsau.6c00796","type":"journal-article","created":{"date-parts":[[2026,8,4]],"date-time":"2026-08-04T14:04:24Z","timestamp":1785852264000},"page":"5145-5153","source":"Crossref","is-referenced-by-count":0,"title":["On-Cycle Enforcement\nin Water: Trimetallic Assemblies\nPreventing Pd Black Formation While Accelerating Selective Suzuki\u2013Miyaura\nCoupling without Olefin Interference"],"prefix":"10.1021","volume":"6","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4982-2449","authenticated-orcid":true,"given":"Sudripet","family":"Sharma","sequence":"first","affiliation":[{"name":"University of Louisville , , , ,","place":["Louisville, Kentucky, United States, 40292"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Uyen","family":"Duong","sequence":"additional","affiliation":[{"name":"University of Louisville , , , ,","place":["Louisville, Kentucky, United States, 40292"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1895-9626","authenticated-orcid":true,"given":"Maarten","family":"Nachtegaal","sequence":"additional","affiliation":[{"name":"PSI , , ,","place":["Villigen, Switzerland, CH-5232"]},{"name":"PSI , , ,","place":["Villigen, Switzerland, CH-5232"]},{"name":"ETH Zu\u0308rich , , ,","place":["Zu\u0308rich, Switzerland, CH-8093"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5478-9639","authenticated-orcid":true,"given":"Adam H.","family":"Clark","sequence":"additional","affiliation":[{"name":"PSI , , ,","place":["Villigen, Switzerland, CH-5232"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ramesh Hiralal","family":"Choudhary","sequence":"additional","affiliation":[{"name":"University of Missouri , , , ,","place":["Columbia, Missouri, United States, 65211"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1297-6145","authenticated-orcid":true,"given":"Jacek B.","family":"Jasinski","sequence":"additional","affiliation":[{"name":"University of Louisville , , , ,","place":["Louisville, Kentucky, United States, 40292"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wilfried","family":"Braje","sequence":"additional","affiliation":[{"name":"AbbVie Deutschland GmbH & Co. KG , , ,","place":["Ludwigshafen, Germany, 67061"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7635-5794","authenticated-orcid":true,"given":"Sachin","family":"Handa","sequence":"additional","affiliation":[{"name":"University of Louisville , , , ,","place":["Louisville, Kentucky, United States, 40292"]},{"name":"University of Missouri , , , ,","place":["Columbia, Missouri, United States, 65211"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,31]]},"reference":[{"key":"2026092808092173400_cit1","doi-asserted-by":"publisher","first-page":"2457","DOI":"10.1021\/cr00039a007","article-title":"Palladium-Catalyzed Cross-Coupling Reactions of Organoboron\nCompounds","volume":"95","author":"Miyaura","year":"1995","journal-title":"Chem. Rev."},{"key":"2026092808092173400_cit2","doi-asserted-by":"publisher","first-page":"2320","DOI":"10.1021\/jo00979a024","article-title":"Palladium-catalyzed vinylic hydrogen substitution reactions\nwith aryl, benzyl, and styryl halides","volume":"37","author":"Heck","year":"1972","journal-title":"J. Org.\nChem."},{"key":"2026092808092173400_cit3","doi-asserted-by":"publisher","first-page":"5062","DOI":"10.1002\/anie.201107017","article-title":"Palladium-catalyzed\ncross-coupling: a historical contextual perspective to the 2010 Nobel\nPrize","volume":"51","author":"Johansson Seechurn","year":"2012","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026092808092173400_cit4","doi-asserted-by":"publisher","first-page":"508","DOI":"10.1002\/anie.198605081","article-title":"The Palladium-Catalyzed\nCross-Coupling Reactions of Organotin Reagents with Organic Electrophiles","volume":"25","author":"Stille","year":"1986","journal-title":"Angew. Chem., Int. Ed. Engl."},{"key":"2026092808092173400_cit5","doi-asserted-by":"publisher","first-page":"4467","DOI":"10.1016\/S0040-4039(00)91094-3","article-title":"A convenient synthesis of acetylenes:\ncatalytic substitutions of acetylenic hydrogen with bromoalkenes,\niodoarenes and bromopyridines","volume":"16","author":"Sonogashira","year":"1975","journal-title":"Tetrahedron Lett."},{"key":"2026092808092173400_cit6","doi-asserted-by":"publisher","first-page":"6554","DOI":"10.1021\/ja031936l","article-title":"Homogeneous Palladium\nCatalyst Suppressing Pd Black Formation in Air Oxidation of Alcohols","volume":"126","author":"Iwasawa","year":"2004","journal-title":"J. Am. Chem. Soc."},{"key":"2026092808092173400_cit7","doi-asserted-by":"publisher","first-page":"19370","DOI":"10.1039\/D5SC04480D","article-title":"Unveiling leaching\u2013oxidizing\u2013landing\npaths of Pd single-atom catalyzed Suzuki\u2013Miyaura reaction by\nambient mass spectrometry","volume":"16","author":"Yin","year":"2025","journal-title":"Chem. Sci."},{"key":"2026092808092173400_cit8","doi-asserted-by":"publisher","first-page":"128","DOI":"10.1039\/b206758g","article-title":"Deactivation processes of homogeneous Pd catalysts\nusing in situ time resolved spectroscopic techniques","volume":"1","author":"Tromp","year":"2003","journal-title":"Chem. Commun."},{"key":"2026092808092173400_cit9","doi-asserted-by":"publisher","first-page":"15751","DOI":"10.1021\/acscatal.4c03690","article-title":"Irreversible\ncatalyst deactivation mechanisms of PdO\/\u03b3-Al2O3 catalysts for\nlean methane oxidation","volume":"14","author":"Chen","year":"2024","journal-title":"ACS Catal."},{"key":"2026092808092173400_cit10","doi-asserted-by":"publisher","first-page":"7080","DOI":"10.1021\/acscatal.4c01699","article-title":"Overcoming Pd catalyst\ndeactivation in the C\u2013H coupling of Tryptophan residues in\nwater using air as the oxidant","volume":"14","author":"Beckers","year":"2024","journal-title":"ACS Catal."},{"key":"2026092808092173400_cit11","doi-asserted-by":"publisher","first-page":"2763","DOI":"10.1039\/D3SC06447F","article-title":"Evidence\nfor Suzuki\u2013Miyaura cross-couplings catalyzed by ligated Pd3-clusters:\nfrom cradle to grave","volume":"15","author":"Jeddi","year":"2024","journal-title":"Chem. Sci."},{"key":"2026092808092173400_cit12","doi-asserted-by":"publisher","first-page":"260","DOI":"10.3390\/inorganics11060260","article-title":"The Fast Formation of a Highly Active\nHomogeneous Catalytic System upon the Soft Leaching of Pd Species\nfrom a Heterogeneous Pd\/C Precursor","volume":"11","author":"Galushko","year":"2023","journal-title":"Inorganics"},{"key":"2026092808092173400_cit13","doi-asserted-by":"publisher","first-page":"9678","DOI":"10.1021\/acscatal.4c02028","article-title":"Deconvoluting Substrates, Support,\nand Temperature\nEffects on Leaching and Deactivation of Pd Catalysts: An In Situ Study\nin Flow","volume":"14","author":"Newton","year":"2024","journal-title":"ACS Catal."},{"key":"2026092808092173400_cit14","doi-asserted-by":"publisher","first-page":"9977","DOI":"10.1039\/D4SC00628C","article-title":"Computational\nanalysis of R\u2013X oxidative addition to Pd nanoparticles","volume":"15","author":"Polynski","year":"2024","journal-title":"Chem. Sci."},{"key":"2026092808092173400_cit15","doi-asserted-by":"publisher","first-page":"11399","DOI":"10.1021\/acscatal.3c01943","article-title":"We already know\neverything about oxidative addition\nto Pd (0): Do we?","volume":"13","author":"Rio","year":"2023","journal-title":"ACS Catal."},{"key":"2026092808092173400_cit16","doi-asserted-by":"publisher","first-page":"16","DOI":"10.3390\/catal15010016","article-title":"Advancements in Pd-Based Supported\nPorous Nanocatalysts\nfor the C\u2013C Cross-Coupling Reactions","volume":"15","author":"Chakraborty","year":"2025","journal-title":"Catalysts"},{"key":"2026092808092173400_cit17","doi-asserted-by":"publisher","first-page":"11615","DOI":"10.1039\/D3CC03855F","article-title":"Photochemical Sonogashira coupling\nreactions: beyond\ntraditional palladium\u2013copper catalysis","volume":"59","author":"Singh","year":"2023","journal-title":"Chem. Commun."},{"key":"2026092808092173400_cit18","doi-asserted-by":"publisher","first-page":"20261","DOI":"10.1021\/am505798y","article-title":"Sonogashira\nCouplings on the Surface of Montmorillonite-Supported Pd\/Cu Nanoalloys","volume":"6","author":"Xu","year":"2014","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"2026092808092173400_cit19","doi-asserted-by":"publisher","first-page":"301","DOI":"10.1021\/jacsau.3c00605","article-title":"Aqueous micelles as solvent, ligand,\nand reaction promoter in catalysis","volume":"4","author":"Virdi","year":"2024","journal-title":"JACS Au"},{"key":"2026092808092173400_cit20","doi-asserted-by":"publisher","first-page":"428","DOI":"10.1016\/j.trechm.2024.06.001","article-title":"The ligand:\nan overlooked element in sustainable catalysis","volume":"6","author":"Handa","year":"2024","journal-title":"Trends Chem."},{"key":"2026092808092173400_cit21","doi-asserted-by":"publisher","first-page":"461","DOI":"10.1038\/nchem.1049","article-title":"Water-oxidation catalysis\nby manganese in a geochemical-like cycle","volume":"3","author":"Hocking","year":"2011","journal-title":"Nat.\nChem."},{"key":"2026092808092173400_cit22","doi-asserted-by":"publisher","first-page":"2330","DOI":"10.1039\/c2sc20226c","article-title":"Layered manganese oxides\nfor water-oxidation: alkaline earth cations influence catalytic activity\nin a photosystem II-like fashion","volume":"3","author":"Wiechen","year":"2012","journal-title":"Chem. Sci."},{"key":"2026092808092173400_cit23","doi-asserted-by":"publisher","first-page":"5037","DOI":"10.1021\/acs.jpcc.0c09806","article-title":"Atom surface dynamics\nof manganese oxide under oxygen evolution reaction-like conditions\nstudied by in situ environmental transmission electron microscopy","volume":"125","author":"Ronge","year":"2021","journal-title":"J. Phys. Chem. C"},{"key":"2026092808092173400_cit24","doi-asserted-by":"publisher","first-page":"2980","DOI":"10.1021\/om049963n","article-title":"Oxidative Addition of Aryl Halides to Palladium(0)\nComplexes: A Density-Functional Study Including Solvation","volume":"23","author":"Senn","year":"2004","journal-title":"Organometallics"},{"key":"2026092808092173400_cit25","doi-asserted-by":"publisher","first-page":"91","DOI":"10.1021\/jacsau.4c00772","article-title":"AshPhos Ligand:\nFacilitating Challenging\nAminations in Five- and Six-Membered Heteroaryl Halides Using Cyclic\nSecondary and Bulky Amines","volume":"5","author":"Dusunge","year":"2025","journal-title":"JACS Au"}],"container-title":["JACS Au"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacsau.6c00796","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jaaucr\/article-pdf\/6\/9\/5145\/66351177\/jacsau.6c00796.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jaaucr\/article-pdf\/6\/9\/5145\/66351177\/jacsau.6c00796.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T12:29:57Z","timestamp":1790598597000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jaaucr\/article\/6\/9\/5145\/5238095\/On-Cycle-Enforcement-in-Water-Trimetallic"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,7,31]]},"references-count":25,"journal-issue":{"issue":"9","published-online":{"date-parts":[[2026,7,31]]},"published-print":{"date-parts":[[2026,9,28]]}},"URL":"https:\/\/doi.org\/10.1021\/jacsau.6c00796","relation":{},"ISSN":["2691-3704"],"issn-type":[{"value":"2691-3704","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,7,31]]}}}