{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,4]],"date-time":"2026-04-04T15:00:53Z","timestamp":1775314853821,"version":"3.50.1"},"reference-count":95,"publisher":"MDPI AG","issue":"11","license":[{"start":{"date-parts":[[2018,11,10]],"date-time":"2018-11-10T00:00:00Z","timestamp":1541808000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["14-43-00017P"],"award-info":[{"award-number":["14-43-00017P"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The mechanism of the addition of indazole (Ind)\u2014a bifunctional aromatic N,NH-nucleophile\u2014to cyclohexyl isocyanide coordinated to the palladium(II) center in the model complex cis-[PdCl2(CNMe)(CNCy)] (1) to give the corresponding aminocarbene ligand was investigated in detail by theoretical (DFT) methods. The most plausible mechanism of this reaction is that of the associative type involving nucleophilic attack of Ind by its unprotonated N atom at the isocyanide carbon atom followed by the stepwise proton transfer from the nucleophile molecule to the isocyanide N atom via deprotonation\/protonation steps. Two reaction channels based on two tautomeric forms of indazole were found. The channel leading to the experimentally isolated aminocarbene product is based on the less stable tautomeric form. Another channel based on the more stable tautomer of Ind is slightly kinetically more favorable but it is endergonic. Thus, the regioselectivity of this reaction is thermodynamically rather than kinetically driven. The bonding situation in key species was analyzed.<\/jats:p>","DOI":"10.3390\/molecules23112942","type":"journal-article","created":{"date-parts":[[2018,11,14]],"date-time":"2018-11-14T02:42:41Z","timestamp":1542163361000},"page":"2942","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Reaction between Indazole and Pd-Bound Isocyanides\u2014A Theoretical Mechanistic Study"],"prefix":"10.3390","volume":"23","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8471-0848","authenticated-orcid":false,"given":"Girolamo","family":"Casella","sequence":"first","affiliation":[{"name":"Dipartimento di Scienze della Terra e del Mare, Universit\u00e0 degli Studi di Palermo, Via Archirafi, 22, 90123 Palermo, Italy"},{"name":"Consorzio Interuniversitario di Ricerca in Chimica dei Metalli nei Sistemi Biologici (C.I.R.C.M.S.B.), Piazza Umberto I, 70121 Bari, Italy"}]},{"given":"Maurizio","family":"Casarin","sequence":"additional","affiliation":[{"name":"Dipartimento di Scienze Chimiche, Universit\u00e0 di Padova, via F. Marzolo 1, 35131 Padova, Italy"}]},{"given":"Vadim Yu.","family":"Kukushkin","sequence":"additional","affiliation":[{"name":"International Group on Organometallic Chemistry, Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab., 7\/9, Saint Petersburg 199034, Russia"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5729-6189","authenticated-orcid":false,"given":"Maxim L.","family":"Kuznetsov","sequence":"additional","affiliation":[{"name":"International Group on Organometallic Chemistry, Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab., 7\/9, Saint Petersburg 199034, Russia"},{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon,  Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2018,11,10]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"2698","DOI":"10.1021\/cr500380d","article-title":"Metal-mediated and metal-catalyzed reactions of isocyanides","volume":"115","author":"Boyarskiy","year":"2015","journal-title":"Chem. Rev."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1007\/s11030-008-9072-1","article-title":"Emerging approaches for the syntheses of bicyclic imidazo[1,2-x]-heterocycles","volume":"12","author":"Hulme","year":"2008","journal-title":"Mol. 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