{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,31]],"date-time":"2026-08-31T18:49:05Z","timestamp":1788202145156,"version":"build-2803163510"},"reference-count":83,"publisher":"Wiley","issue":"32","license":[{"start":{"date-parts":[[2023,4,27]],"date-time":"2023-04-27T00:00:00Z","timestamp":1682553600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100006770","name":"American Chemical Society Petroleum Research Fund","doi-asserted-by":"publisher","award":["61891-DNI4"],"award-info":[{"award-number":["61891-DNI4"]}],"id":[{"id":"10.13039\/100006770","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2023,6,7]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    The reactions of elemental sulfur (S\n                    <jats:sub>8<\/jats:sub>\n                    ) and polysulfides with nucleophiles are relevant to organic synthesis, materials science and biochemistry, but the mechanisms by which they operate are still unknown due to the inherent thermodynamic and kinetic instability of polysulfide intermediates. Using Density Functional Theory (DFT) calculations at the \u03c9B97X\u2010D\/aug\u2010cc\u2010pV(T+\n                    <jats:italic>d<\/jats:italic>\n                    )Z\/SMD(MeCN) \/\/ \u03c9B97X\u2010D\/aug\u2010cc\u2010pVDZ\/SMD(MeCN) level of theory, we studied the mechanisms behind the reaction of elemental sulfur and polysulfides with cyanide and phosphines, which quantitatively generate the monosulfide products thiocyanate and phosphine sulfides, respectively. All plausible pathways including nucleophilic decomposition, unimolecular decomposition, scrambling reactions, and attack on thiosulfoxides, have been considered to provide the first comprehensive mechanistic picture for this class of reactions. Overall, intramolecular cyclization is identified as the most favorable decomposition pathway for long polysulfides. For short polysulfides, a mixture of unimolecular decomposition, nucleophilic attack, and scrambling pathways can be expected.\n                  <\/jats:p>","DOI":"10.1002\/chem.202203906","type":"journal-article","created":{"date-parts":[[2023,4,3]],"date-time":"2023-04-03T08:36:03Z","timestamp":1680510963000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":20,"title":["Mechanisms of the Reaction of Elemental Sulfur and Polysulfides with Cyanide and Phosphines**"],"prefix":"10.1002","volume":"29","author":[{"given":"Jyoti","family":"Sharma","sequence":"first","affiliation":[{"name":"Department of Chemistry and Environmental Science New Jersey Institute of Technology  Newark NJ USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0546-7537","authenticated-orcid":false,"given":"Pier Alexandre","family":"Champagne","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Environmental Science New Jersey Institute of Technology  Newark NJ USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,4,27]]},"reference":[{"key":"e_1_2_9_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201601329"},{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.202000535"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c09329"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-019-08430-8"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41557-022-01049-1"},{"key":"e_1_2_9_6_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CS00826D"},{"key":"e_1_2_9_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscentsci.0c00449"},{"key":"e_1_2_9_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/1873-3468.13090"},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1155\/2020\/8294158"},{"key":"e_1_2_9_10_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.freeradbiomed.2014.09.007"},{"key":"e_1_2_9_11_1","doi-asserted-by":"publisher","DOI":"10.1089\/ars.2017.7076"},{"key":"e_1_2_9_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr60301a003"},{"key":"e_1_2_9_13_1","doi-asserted-by":"publisher","DOI":"10.1002\/jlac.18571040102"},{"key":"e_1_2_9_14_1","doi-asserted-by":"publisher","DOI":"10.1039\/jr9350001786"},{"key":"e_1_2_9_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01596a043"},{"key":"e_1_2_9_16_1","first-page":"275","volume":"8","author":"Watson H. 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