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The inactivation of thiol\u2010based enzymes, promoted by the strong affinity binding of electrophilic mercuric ions to thiol and selenol groups of proteins, is likely an important factor explaining its toxicity. A key role is played by the chemistry and reactivity of the mercury\u2013chalcogens bond, particularly Hg\uf8ffS and Hg\uf8ffSe, which is the focus of this computational work (level of theory: (COSMO)\u2010ZORA\u2010BLYP\u2010D3(BJ)\/TZ2P). We analyze nine ligand\u2010exchange model reactions (the so\u2010called Rabenstein's reactions) involving an entering ligand (methylchalcogenolate) and a substrate (methylchalcogenolatemethylmercury). Trends in reaction and activation energies are discussed and a change in mechanism is reported for all cases when going from gas phase to water, that is, from a single\u2010well potential energy surface (PES) to a canonical S<jats:sub>N<\/jats:sub>2\u2010like mechanism. The reasons accounting for the biochemically challenging and desired displacement of methylmercury from a seleno\/thiol protein can be found already in these model reactions, as can be seen from the similarities of the ligand exchange reactions in solution in thermodynamics and kinetics.<\/jats:p>","DOI":"10.1002\/jcc.26371","type":"journal-article","created":{"date-parts":[[2020,7,13]],"date-time":"2020-07-13T08:36:52Z","timestamp":1594629412000},"page":"2045-2054","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":27,"title":["Chalcogen\u2013mercury bond formation and disruption in model Rabenstein's reactions: A computational analysis"],"prefix":"10.1002","volume":"41","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0407-0263","authenticated-orcid":false,"given":"Andrea","family":"Madabeni","sequence":"first","affiliation":[{"name":"Dipartimento di Scienze Chimiche Universit\u00e0 Degli Studi di Padova  Padova Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3442-7654","authenticated-orcid":false,"given":"Marco","family":"Dalla Tiezza","sequence":"additional","affiliation":[{"name":"Dipartimento di Scienze Chimiche Universit\u00e0 Degli Studi di Padova  Padova Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9750-5034","authenticated-orcid":false,"given":"Folorunsho Bright","family":"Omage","sequence":"additional","affiliation":[{"name":"Departamento de Bioqu\u00edmica e Biologia Molecular Universidade Federal de Santa Maria  Santa Maria Rio Grande do Sul Brazil"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9133-6102","authenticated-orcid":false,"given":"Pablo Andrei","family":"Nogara","sequence":"additional","affiliation":[{"name":"Dipartimento di Scienze Chimiche Universit\u00e0 Degli Studi di Padova  Padova Italy"},{"name":"Departamento de Bioqu\u00edmica e Biologia Molecular Universidade Federal de Santa Maria  Santa Maria Rio Grande do Sul Brazil"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5506-6347","authenticated-orcid":false,"given":"Marco","family":"Bortoli","sequence":"additional","affiliation":[{"name":"Dipartimento di Scienze Chimiche Universit\u00e0 Degli Studi di Padova  Padova Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3829-0595","authenticated-orcid":false,"given":"Jo\u00e3o Batista Teixeira","family":"Rocha","sequence":"additional","affiliation":[{"name":"Departamento de Bioqu\u00edmica e Biologia Molecular Universidade Federal de Santa Maria  Santa Maria Rio Grande do Sul Brazil"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1673-5111","authenticated-orcid":false,"given":"Laura","family":"Orian","sequence":"additional","affiliation":[{"name":"Dipartimento di Scienze Chimiche Universit\u00e0 Degli Studi di Padova  Padova Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2020,7,13]]},"reference":[{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1289\/ehp.1104494"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.3961\/jpmph.2012.45.6.353"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.freeradbiomed.2009.05.013"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.bbagen.2019.01.006"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.bbagen.2018.11.007"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.bbagen.2019.01.007"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0006-3061(00)80237-9"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic00177a016"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/ed055p292"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic00234a030"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1002\/cphc.201700743"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.freeradbiomed.2015.06.011"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.bbagen.2012.11.020"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.bbagen.2009.01.014"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.bbagen.2009.02.014"},{"key":"e_1_2_7_17_1","first-page":"103","volume-title":"Methods in Enzymology","author":"Parks J. 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