{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,25]],"date-time":"2026-09-25T04:31:23Z","timestamp":1790310683765,"version":"4.1.0"},"reference-count":105,"publisher":"MDPI AG","issue":"7","license":[{"start":{"date-parts":[[2017,7,8]],"date-time":"2017-07-08T00:00:00Z","timestamp":1499472000000},"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>Despite the long history of the investigation of nucleophilic addition to metal-bound isocyanides, some important aspects of the reaction mechanism remain unclear even for the simplest systems. In this work, the addition of the sp3-N, sp2-N, and mixed sp2\/sp3-N nucleophiles (i.e., HNMe2, HN=CPh2, and H2N\u2013N=CPh2, respectively) to isocyanides C\u2261NR coordinated to the platinum(II) centers in the complexes cis-[Pt(C\u2261NCy)(2-pyz)(dppe)]+ (2-pyz = 2-pyrazyl, dmpe = Me2PCH2CH2PMe2) and cis-[PtCl2(C\u2261NXyl)(C\u2261NMe)] was studied in detail by theoretical (DFT) methods. The mechanism of these reactions is stepwise associative rather than concerted and it includes the addition of a nucleophile to the isocyanide C atom, deprotonation of the nucleophilic moiety in the resulting intermediate, and protonation of the isocyanide N atom to give the final product. The calculated activation energy (\u0394G\u2260) of all reactions is in the range of 19.8\u201322.4 kcal\/mol.<\/jats:p>","DOI":"10.3390\/molecules22071141","type":"journal-article","created":{"date-parts":[[2017,7,10]],"date-time":"2017-07-10T11:05:31Z","timestamp":1499684731000},"page":"1141","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Metal-Mediated Addition of N-Nucleophiles to Isocyanides: Mechanistic Aspects"],"prefix":"10.3390","volume":"22","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5729-6189","authenticated-orcid":false,"given":"Maxim","family":"Kuznetsov","sequence":"first","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, Lisbon 1049-001, Portugal"},{"name":"International Group on Organometallic Chemistry, Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab., 7\/9, Saint Petersburg 199034, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Vadim","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"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2017,7,8]]},"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. 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