{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T15:45:11Z","timestamp":1789487111910,"version":"build-2803163510"},"reference-count":94,"publisher":"Wiley","issue":"24","license":[{"start":{"date-parts":[[2026,9,11]],"date-time":"2026-09-11T00:00:00Z","timestamp":1789084800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,9,11]],"date-time":"2026-09-11T00:00:00Z","timestamp":1789084800000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["25\u201013\u201000387"],"award-info":[{"award-number":["25\u201013\u201000387"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["J Comput Chem"],"published-print":{"date-parts":[[2026,9,15]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    The evolution of catalytic systems based on transition metal complexes under catalytic reaction conditions leads to the formation of a catalyst cocktail, i.e., an ensemble of species with different structures, each capable of exhibiting catalytic activity. Transformation of molecular Pd(II)\u2013NHC complexes into a catalytically active cocktail form involves R\u2013NHC coupling, which results in the formation of low\u2010coordinated metal centers and [R\u2013NHC]\n                    <jats:sup>(+)<\/jats:sup>\n                    [\n                    <jats:italic>X<\/jats:italic>\n                    ]\n                    <jats:sup>(\u2212)<\/jats:sup>\n                    salt (\n                    <jats:italic>X<\/jats:italic>\n                    \u2009=\u2009halogen). In this work, using DFT methods, it is demonstrated that one factor influencing the R\u2013NHC coupling process is substituent effects within the pyridine or phosphine ligand of the Pd(II) complex (\n                    <jats:italic>R<\/jats:italic>\n                    \u2009=\u2009Me, Ph; NHC\u2009=\u2009IMe, IPr, IMes). The presence of electron\u2010donating (\u2013OMe) or electron\u2010withdrawing (\u2013CN; \u2013F) substituents in the ligand molecule significantly influences both the activation energy and the reaction energy of the R\u2013NHC coupling process. In particular, electron\u2010accepting substituents reduce the potential barrier for this process and completely shift the equilibrium toward the product of the R\u2013NHC coupling, whereas electron\u2010donating substituents possess the opposite effect. Thus, the effect of substituents can act as a \u201cswitch\u201d facilitating the transition from molecular catalysis to \u201ccocktail\u2010type\u201d catalysis.\n                  <\/jats:p>","DOI":"10.1002\/jcc.70500","type":"journal-article","created":{"date-parts":[[2026,9,12]],"date-time":"2026-09-12T01:50:42Z","timestamp":1789177842000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Substituent Effects on the Stability of Pd\u2013\n                    <scp>NHC<\/scp>\n                    Complexes: Switching From Molecular to \u201cCocktail\u2010Type\u201d Catalysis"],"prefix":"10.1002","volume":"47","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5446-3527","authenticated-orcid":false,"given":"Vladislav O.","family":"Naumovich","sequence":"first","affiliation":[{"name":"N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences  Moscow Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0545-5720","authenticated-orcid":false,"given":"Evgeniy G.","family":"Gordeev","sequence":"additional","affiliation":[{"name":"N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences  Moscow Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6447-557X","authenticated-orcid":false,"given":"Valentine P.","family":"Ananikov","sequence":"additional","affiliation":[{"name":"N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences  Moscow Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,9,11]]},"reference":[{"key":"e_1_2_10_2_1","doi-asserted-by":"publisher","DOI":"10.1038\/nature13384"},{"key":"e_1_2_10_3_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41570\u2010021\u201000321\u20101"},{"key":"e_1_2_10_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527609451"},{"key":"e_1_2_10_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/C1CS15088J"},{"key":"e_1_2_10_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr800501s"},{"key":"e_1_2_10_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr900074m"},{"key":"e_1_2_10_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.196801412"},{"key":"e_1_2_10_9_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022\u2010328X(00)88691\u2010X"},{"key":"e_1_2_10_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00001a054"},{"key":"e_1_2_10_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199523711"},{"key":"e_1_2_10_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr9903048"},{"key":"e_1_2_10_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/B914618K"},{"key":"e_1_2_10_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr00039a007"},{"key":"e_1_2_10_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar800036s"},{"key":"e_1_2_10_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200601663"},{"key":"e_1_2_10_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.202000911"},{"key":"e_1_2_10_18_1","doi-asserted-by":"publisher","DOI":"10.1016\/S1872\u20102067(15)60843\u20109"},{"key":"e_1_2_10_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.6b00512"},{"key":"e_1_2_10_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5c00088"},{"key":"e_1_2_10_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201400040"},{"key":"e_1_2_10_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/asia.201501405"},{"key":"e_1_2_10_23_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41586\u2010023\u201006087\u20104"},{"key":"e_1_2_10_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5c01435"},{"key":"e_1_2_10_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacsau.4c00784"},{"key":"e_1_2_10_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja042491j"},{"key":"e_1_2_10_27_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929\u2010021\u201000607\u2010z"},{"key":"e_1_2_10_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201106131"},{"key":"e_1_2_10_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja049759r"},{"key":"e_1_2_10_30_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2024.215897"},{"key":"e_1_2_10_31_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200600251"},{"key":"e_1_2_10_32_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200600206"},{"key":"e_1_2_10_33_1","doi-asserted-by":"publisher","DOI":"10.1021\/op400278d"},{"key":"e_1_2_10_34_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2025.122915"},{"key":"e_1_2_10_35_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.molcata.2016.12.001"},{"key":"e_1_2_10_36_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2016.12.021"},{"key":"e_1_2_10_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/om201120n"},{"key":"e_1_2_10_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.5c00117"},{"key":"e_1_2_10_39_1","doi-asserted-by":"publisher","DOI":"10.1016\/S1872\u20102067(25)64824\u20108"},{"key":"e_1_2_10_40_1","doi-asserted-by":"publisher","DOI":"10.3390\/chemistry7040109"},{"key":"e_1_2_10_41_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3CY00865G"},{"key":"e_1_2_10_42_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1CY01601F"},{"key":"e_1_2_10_43_1","doi-asserted-by":"publisher","DOI":"10.26434\/chemrxiv\u20102025\u20106pl69"},{"key":"e_1_2_10_44_1","doi-asserted-by":"publisher","DOI":"10.59761\/RCR5181"},{"key":"e_1_2_10_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.4c02585"},{"key":"e_1_2_10_46_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.checat.2024.101255"},{"key":"e_1_2_10_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c05294"},{"key":"e_1_2_10_48_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.2c03345"},{"key":"e_1_2_10_49_1","doi-asserted-by":"publisher","DOI":"10.1039\/B811449H"},{"key":"e_1_2_10_50_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0SC02629H"},{"key":"e_1_2_10_51_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.25572"},{"key":"e_1_2_10_52_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.7b00184"},{"key":"e_1_2_10_53_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic061926w"},{"key":"e_1_2_10_54_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja003861g"},{"key":"e_1_2_10_55_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.oprd.0c00548"},{"key":"e_1_2_10_56_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9GC01043B"},{"key":"e_1_2_10_57_1","doi-asserted-by":"publisher","DOI":"10.1002\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