{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,26]],"date-time":"2026-07-26T18:50:39Z","timestamp":1785091839076,"version":"3.55.0"},"reference-count":79,"publisher":"Wiley","issue":"4","license":[{"start":{"date-parts":[[2025,12,14]],"date-time":"2025-12-14T00:00:00Z","timestamp":1765670400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2025,12,14]],"date-time":"2025-12-14T00:00:00Z","timestamp":1765670400000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2026,1,23]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    Experimental catalyst design to promote the hydrogenation of CO\n                    <jats:sub>2<\/jats:sub>\n                    has led to the synthesis of an efficient tripodal palladium pincer complex. This work presents a computational reading key of the ligand design for efficient transition metal catalysts using palladium pincer complexes as precise representatives. By investigating the electronic structure\/reactivity relationship, we demonstrate that all the progressive adjustments of the pincer architecture do not significantly affect the Pd\u2010L (L = PCy\n                    <jats:sub>3<\/jats:sub>\n                    , PPh\n                    <jats:sub>3<\/jats:sub>\n                    ) bond and the electron density rearrangement in the first coordination sphere of the complex. We find a strong Pd\u2010L bond, where the dispersion energy contribution is substantial, that rules out the previously proposed mechanism involving Pd\u2010L bond breaking. Mechanisms of H\n                    <jats:sub>2<\/jats:sub>\n                    activation and CO\n                    <jats:sub>2<\/jats:sub>\n                    reduction are revisited, which showcase how the secondary coordination sphere plays a critical role in reactivity, strongly affecting the Pd\u2010O (carboxylic arm) bond polarization due to hydrogen bond formation with the O atom. The catalytically active complex is demonstrated to perform through a stepwise mechanism involving polar addition of H\n                    <jats:sub>2<\/jats:sub>\n                    across the Pd\n                    <jats:sup>\u03b4+<\/jats:sup>\n                    \u2010O\n                    <jats:sup>\u03b4\u2212<\/jats:sup>\n                    bond and subsequent OH deprotonation by an external base (DBU), forming a Pd\u2010H hydride complex, which easily reacts with CO\n                    <jats:sub>2<\/jats:sub>\n                    through an outer\u2010sphere hydride transfer path.\n                  <\/jats:p>","DOI":"10.1002\/chem.202503263","type":"journal-article","created":{"date-parts":[[2025,12,15]],"date-time":"2025-12-15T05:54:22Z","timestamp":1765778062000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Computational Understanding of Catalyst Design: Palladium Pincer Complexes for Carbon Dioxide Hydrogenation"],"prefix":"10.1002","volume":"32","author":[{"given":"Chiara","family":"Pietracci","sequence":"first","affiliation":[{"name":"Department of Chemistry Biology and Biotechnology University of Perugia  Perugia Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Leonardo","family":"Belpassi","sequence":"additional","affiliation":[{"name":"CNR Institute of Chemical Science and Technologies \u201cGiulio Natta\u201d (CNR\u2010SCITEC)  Perugia Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1286-9294","authenticated-orcid":false,"given":"Paola","family":"Belanzoni","sequence":"additional","affiliation":[{"name":"Department of Chemistry Biology and Biotechnology University of Perugia  Perugia Italy"},{"name":"CNR Institute of Chemical Science and Technologies \u201cGiulio Natta\u201d (CNR\u2010SCITEC)  Perugia Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,12,14]]},"reference":[{"key":"e_1_2_7_2_1","unstructured":"Webpage https:\/\/science.nasa.gov\/earth\/explore\/earth\u2010indicators\/carbon\u2010dioxide."},{"key":"e_1_2_7_3_1","unstructured":"Webpage https:\/\/gml.noaa.gov\/ccgg\/trends\/monthly.html."},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-023-42079-8"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.adn9388"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcat.2016.04.003"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2012.12.035"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar5002457"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5DT02295A"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5DT04429D"},{"key":"e_1_2_7_11_1","first-page":"179","volume":"54","author":"Melen R. 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