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The electron donating\/withdrawing capacity of the ligand was screened through the incorporation of various substituents such as halogens, nitro, alkoxides, ketones, esters, amines, and amides. Variations in structural parameters, energy barriers for the Ru\u2212O bond dissociation, and Ru\u2212O bond strength were examined as a function of the Hammett constant. It was found that electronic properties of the catalysts such as chemical potential, hardness, and electrophilicity correlate linearly with the dissociative energy barriers. These findings enable a systematic rationalization and prediction of rate of precatalyst initiation through the calculation of only the HOMO\u2010LUMO gap of catalysts, as the faster the initiation, the more electrophilic the catalyst.<\/jats:p>","DOI":"10.1002\/cphc.202200580","type":"journal-article","created":{"date-parts":[[2022,9,5]],"date-time":"2022-09-05T07:28:53Z","timestamp":1662362933000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":13,"title":["Electrophilicity of Hoveyda\u2010Grubbs Olefin Metathesis Catalysts as the Driving Force that Controls Initiation Rates"],"prefix":"10.1002","volume":"23","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6589-790X","authenticated-orcid":false,"given":"Juan Pablo","family":"Mart\u00ednez","sequence":"first","affiliation":[{"name":"Centre of New Technologies University of Warsaw  02-097 Warszawa Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2385-1476","authenticated-orcid":false,"given":"Bartosz","family":"Trzaskowski","sequence":"additional","affiliation":[{"name":"Centre of New Technologies University of Warsaw  02-097 Warszawa Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,10,19]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/i360011a002"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)89881-6"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/0304-5102(80)87006-4"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00533a035"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00166a023"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00213a014"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201102012"},{"key":"e_1_2_8_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201102012"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CS00027A"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2013.05.041"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.oprd.7b00319"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)88691-X"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.196801412"},{"key":"e_1_2_8_12_2","first-page":"152","volume":"80","year":"1968","journal-title":"Angew. 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