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It reacts within minutes with even the most sterically demanding ligands to form monoligated Pd complexes and, upon exposure to nucleophiles, including weak, non\u2010reducing\n                    <jats:italic>N<\/jats:italic>\n                    \u2010nucleophiles, rapidly generates reactive Pd(0) species with the release of inert naphthalene derivatives. Across 15 representative transformations, catalysts generated in situ from [Pd(1\u2010MeNAP)TFA]\n                    <jats:sub>2<\/jats:sub>\n                    enable substantial reductions in reaction temperature, often by 80\u00b0C, while preserving established ligands and reaction conditions, thereby providing a drop\u2010in solution to existing reactivity limitations. As a result, arylations of amides, carbamates, sulfonamides, amidines, ureas, cyclopropylamines, and trifluoroethylamines can be performed at room\u2010temperature with markedly improved functional\u2010group tolerance and compatibility with sensitive, coordinating heterocycles. Mechanistic studies reveal that catalyst activation, rather than catalytic turnover, has been the principal bottleneck in many cross\u2010coupling reactions.\n                  <\/jats:p>","DOI":"10.1002\/anie.3359287","type":"journal-article","created":{"date-parts":[[2026,5,13]],"date-time":"2026-05-13T14:59:46Z","timestamp":1778684386000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Unlocking Catalyst Activation as a Critical Bottleneck in Cross\u2010Coupling Reactions: Room\u2010Temperature Couplings of Weak Nucleophiles Enabled by [Pd(1\u2010MeNAP)TFA]\n                    <sub>2<\/sub>\n                    Precatalysts"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0009-0003-4734-445X","authenticated-orcid":false,"given":"Sourav","family":"Manna","sequence":"first","affiliation":[{"name":"Chair of Organic Chemistry I, Faculty of Chemistry and Biochemistry Ruhr\u2010Universit\u00e4t Bochum  Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Henric F.","family":"Janning","sequence":"additional","affiliation":[{"name":"Chair of Organic Chemistry I, Faculty of Chemistry and Biochemistry Ruhr\u2010Universit\u00e4t Bochum  Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1718-0207","authenticated-orcid":false,"given":"Nikolaos V.","family":"Tzouras","sequence":"additional","affiliation":[{"name":"Chair of Organic Chemistry I, Faculty of Chemistry and Biochemistry Ruhr\u2010Universit\u00e4t Bochum  Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jane Anto Simplica","family":"Sagayaraj","sequence":"additional","affiliation":[{"name":"Chair of Organic Chemistry I, Faculty of Chemistry and Biochemistry Ruhr\u2010Universit\u00e4t Bochum  Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fadil Faizal","family":"Mannighayil","sequence":"additional","affiliation":[{"name":"Chair of Organic Chemistry I, Faculty of Chemistry and Biochemistry Ruhr\u2010Universit\u00e4t Bochum  Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Angelino","family":"Doppiu","sequence":"additional","affiliation":[{"name":"Precious Metals Chemistry Umicore AG &amp; Co. KG  Hanau\u2010Wolfgang Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2547-3037","authenticated-orcid":false,"given":"Lukas J.","family":"Goo\u00dfen","sequence":"additional","affiliation":[{"name":"Chair of Organic Chemistry I, Faculty of Chemistry and Biochemistry Ruhr\u2010Universit\u00e4t Bochum  Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,5,13]]},"reference":[{"key":"e_1_2_5_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201107017"},{"key":"e_1_2_5_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jafc.8b03792"},{"key":"e_1_2_5_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.4c02573"},{"key":"e_1_2_5_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.2c00204"},{"key":"e_1_2_5_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200461189"},{"key":"e_1_2_5_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/ijch.201900167"},{"key":"e_1_2_5_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/om00004a039"},{"key":"e_1_2_5_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol801285g"},{"key":"e_1_2_5_10_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201210252"},{"key":"e_1_2_5_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201601450"},{"key":"e_1_2_5_12_1","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.202400358"},{"key":"e_1_2_5_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.oprd.9b00214"},{"key":"e_1_2_5_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/om201217r"},{"key":"e_1_2_5_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200600206"},{"key":"e_1_2_5_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/om020804i"},{"key":"e_1_2_5_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo2013324"},{"key":"e_1_2_5_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol0260831"},{"key":"e_1_2_5_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo901121e"},{"key":"e_1_2_5_20_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202110450"},{"key":"e_1_2_5_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/om2005222"},{"key":"e_1_2_5_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201104009"},{"key":"e_1_2_5_23_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200902842"},{"key":"e_1_2_5_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo101187q"},{"key":"e_1_2_5_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b03215"},{"key":"e_1_2_5_26_1","doi-asserted-by":"publisher","DOI":"10.1039\/C2SC20903A"},{"key":"e_1_2_5_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.5b00878"},{"key":"e_1_2_5_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo500355k"},{"key":"e_1_2_5_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/cs502011x"},{"key":"e_1_2_5_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja983939h"},{"key":"e_1_2_5_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.1c00288"},{"key":"e_1_2_5_32_1","unstructured":"W.\u2010J.He W.\u2010Z.Qin S.Yang et\u00a0al. \u201cChemRxiv preprint \u201d (2024) https:\/\/doi.org\/10.26434\/chemrxiv\u20102024\u2010sj081."},{"key":"e_1_2_5_33_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0010\u20108545(98)00073\u20103"},{"key":"e_1_2_5_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja2102373"},{"key":"e_1_2_5_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.5b01005"},{"key":"e_1_2_5_36_1","doi-asserted-by":"publisher","DOI":"10.1002\/ijch.201900067"},{"key":"e_1_2_5_37_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41570\u2010017\u20100025"},{"key":"e_1_2_5_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.4c02624"},{"key":"e_1_2_5_39_1","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.202300761"},{"key":"e_1_2_5_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja412565c"},{"key":"e_1_2_5_41_1","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.202000987"},{"key":"e_1_2_5_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja057704z"},{"key":"e_1_2_5_43_1","doi-asserted-by":"publisher","DOI":"10.1039\/C3972000629A"},{"key":"e_1_2_5_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.7b01082"},{"key":"e_1_2_5_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.1c02307"},{"key":"e_1_2_5_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.4c00125"},{"key":"e_1_2_5_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.5c00039"},{"key":"e_1_2_5_48_1","doi-asserted-by":"publisher","DOI":"10.1039\/b811772a"},{"key":"e_1_2_5_49_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.70908"},{"key":"e_1_2_5_50_1","unstructured":"Deposition numbers 2526679 (forIaTFA) and 2526680 for [Pd(1\u2010MeNAP)(H2O)2] [OTs] contain the supplementary crystallographic data for this paper. 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