{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,9]],"date-time":"2026-04-09T17:02:04Z","timestamp":1775754124872,"version":"3.50.1"},"reference-count":31,"publisher":"Wiley","issue":"1","license":[{"start":{"date-parts":[[2025,12,18]],"date-time":"2025-12-18T00:00:00Z","timestamp":1766016000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2025,12,18]],"date-time":"2025-12-18T00:00:00Z","timestamp":1766016000000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["J Comput Chem"],"published-print":{"date-parts":[[2026,1,5]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    The methanolysis of urea represents a promising green route for the synthesis of dimethyl carbonate (DMC), a versatile compound with applications in sustainable chemistry and energy storage. In this work, a comprehensive quantum chemical investigation of the reaction mechanism is presented using density functional theory (DFT), focusing on both uncatalyzed and organotin\u2010catalyzed systems, considering both stepwise and concerted pathways. For MC production, both the stepwise and the concerted mechanisms mediated by a methanol dimer exhibit the lowest activation enthalpies. Consequently, an effective activation enthalpy of 24.0\u2009kcal\/mol was determined, in excellent agreement with the experimental value of 23.45\u2009kcal\/mol. In contrast, the bimolecular stepwise and concerted models exhibited higher barriers (\u0394\n                    <jats:italic>H<\/jats:italic>\n                    <jats:sup>\u2021<\/jats:sup>\n                    \u2009\u2248\u200942\u201352\u2009kcal\/mol). Entropy values indicated that mechanisms with two methanol molecules involve higher preorganization (\u0394\n                    <jats:italic>S<\/jats:italic>\n                    <jats:sup>\u2021<\/jats:sup>\n                    \u2009\u2248\u2009\u221260\u2009cal\/mol\u2009K), compared to \u221230\u2009cal\/mol\u2009K in single\u2010molecule pathways. For DMC production from the methyl carbamate intermediate, the rate\u2010limiting step, it was analyzed with and without an organotin catalyst. Catalysis lowers the activation enthalpy by approximately 10\u2009kcal\/mol, yielding a value of 24.9\u2009kcal\/mol for the methanol monomer catalyzed system, in good agreement with the experimental \u0394\n                    <jats:italic>H<\/jats:italic>\n                    <jats:sup>\u2021<\/jats:sup>\n                    of 24.3\u2009kcal\/mol. To deepen mechanistic understanding, we employed advanced quantum descriptors including reaction force analysis, reaction electronic flux (REF), and natural bond orbital (NBO) charge evolution. These tools revealed synchronous bond rearrangements and electronic polarization effects that govern transition state stability, mainly by the electronic charges of the carbon atom in the carbonyl group and the amine group in the sense C\n                    <jats:sup>\u03b4+<\/jats:sup>\n                    \u2014N\n                    <jats:sup>\u03b4\u2010<\/jats:sup>\n                    . This study provides novel mechanistic insights into the dual role of hydrogen bonding and Lewis acid catalysis in DMC synthesis and demonstrates the utility of quantum chemical tools in elucidating complex reaction pathways, offering a foundation for rational catalyst design.\n                  <\/jats:p>","DOI":"10.1002\/jcc.70299","type":"journal-article","created":{"date-parts":[[2025,12,19]],"date-time":"2025-12-19T07:35:16Z","timestamp":1766129716000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Quantum Chemical Characterization of Urea Methanolysis: Mechanistic Pathways and Organotin\u2010Catalyzed\n                    <scp>DMC<\/scp>\n                    Formation"],"prefix":"10.1002","volume":"47","author":[{"ORCID":"https:\/\/orcid.org\/0009-0004-8703-8024","authenticated-orcid":false,"given":"Daniel","family":"Martinez\u2010Arias","sequence":"first","affiliation":[{"name":"Department of Chemical Engineering Universidad San Francisco de Quito  Quito Ecuador"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6128-9504","authenticated-orcid":false,"given":"Jos\u00e9 R.","family":"Mora","sequence":"additional","affiliation":[{"name":"Department of Chemical Engineering Universidad San Francisco de Quito  Quito Ecuador"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0009-0008-4023-8810","authenticated-orcid":false,"given":"Vladimir","family":"Rodriguez","sequence":"additional","affiliation":[{"name":"Department of Mathematics Universidad San Francisco de Quito  Quito Ecuador"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7503-1528","authenticated-orcid":false,"given":"Edgar A.","family":"Marquez","sequence":"additional","affiliation":[{"name":"Chemistry and Biology Research Group, Department of Chemistry and Biology, Faculty of Basic Sciences Universidad del Norte  Barranquilla Colombia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0592-8652","authenticated-orcid":false,"given":"Patricio J.","family":"Espinoza\u2010Montero","sequence":"additional","affiliation":[{"name":"School of Chemical Sciences Pontificia Universidad Cat\u00f3lica del Ecuador  Quito Ecuador"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6177-7919","authenticated-orcid":false,"given":"Jos\u00e9 L.","family":"Paz","sequence":"additional","affiliation":[{"name":"Departamento Acad\u00e9mico de Qu\u00edmica Inorg\u00e1nica, Facultad de Qu\u00edmica e Ingenier\u00eda Qu\u00edmica Universidad Nacional Mayor de San Marcos  Lima Peru"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2721-1142","authenticated-orcid":false,"given":"Yovani","family":"Marrero\u2010Ponce","sequence":"additional","affiliation":[{"name":"Grupo de Medicina Molecular y Traslacional (MeM&amp;T) Colegio de Ciencias de la Salud (COCSA), Escuela de Medicina, Edificio de Especialidades M\u00e9dicas, Diego de Robles y v\u00eda Interoce\u00e1nica, Universidad San Francisco de Quito (USFQ)  Quito Pichincha Ecuador"},{"name":"Facultad de Ingenier\u00eda Universidad Panamericana  Ciudad de M\u00e9xico Mexico"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2025,12,18]]},"reference":[{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.catcom.2019.01.005"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cjche.2018.12.003"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cherd.2021.10.029"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cej.2021.132378"},{"key":"e_1_2_9_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jiec.2023.05.015"},{"key":"e_1_2_9_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cplett.2021.139196"},{"key":"e_1_2_9_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jct.2021.106473"},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.molcata.2003.09.041"},{"key":"e_1_2_9_10_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(97)00787-0"},{"key":"e_1_2_9_11_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cej.2004.07.003"},{"issue":"7","key":"e_1_2_9_12_1","first-page":"780","article-title":"Carbon Dioxide Conversion to Dimethyl Carbonate: The Effect of Silica as Support for SnO2 and ZrO2 Catalysts","volume":"14","author":"Ballivet\u2010Tkatchenko D.","year":"2011","journal-title":"Comptes Rendus Chimie"},{"key":"e_1_2_9_13_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcou.2023.102509"},{"key":"e_1_2_9_14_1","doi-asserted-by":"publisher","DOI":"10.1016\/B978-0-443-15740-0.00086-0"},{"key":"e_1_2_9_15_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.mencom.2016.11.012"},{"key":"e_1_2_9_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.24891"},{"key":"e_1_2_9_17_1","volume-title":"Gaussian 16, Revision C.01","author":"Frisch M. J.","year":"2016"},{"key":"e_1_2_9_18_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.462066"},{"key":"e_1_2_9_19_1","doi-asserted-by":"publisher","DOI":"10.1080\/00268976.2021.1995064"},{"key":"e_1_2_9_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp011945l"},{"key":"e_1_2_9_21_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.448975"},{"key":"e_1_2_9_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00122a028"},{"key":"e_1_2_9_23_1","doi-asserted-by":"publisher","DOI":"10.3390\/ijms22136876"},{"key":"e_1_2_9_24_1","doi-asserted-by":"publisher","DOI":"10.1002\/qua.21715"},{"key":"e_1_2_9_25_1","doi-asserted-by":"publisher","DOI":"10.1002\/cjce.5450520612"},{"key":"e_1_2_9_26_1","doi-asserted-by":"publisher","DOI":"10.1007\/s10562-019-03075-0"},{"key":"e_1_2_9_27_1","doi-asserted-by":"publisher","DOI":"10.1107\/S010876818400210X"},{"key":"e_1_2_9_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1097-0134(199706)28:2<144::AID-PROT2>3.0.CO;2-F"},{"key":"e_1_2_9_29_1","volume-title":"Advances in Quantum Chemistry","author":"Lendvay G.","year":"2025"},{"key":"e_1_2_9_30_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.comptc.2019.02.003"},{"key":"e_1_2_9_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp805225e"},{"key":"e_1_2_9_32_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CS00210E"}],"container-title":["Journal of Computational Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/jcc.70299","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/jcc.70299","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/jcc.70299","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,4,9]],"date-time":"2026-04-09T16:11:08Z","timestamp":1775751068000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/jcc.70299"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,12,18]]},"references-count":31,"journal-issue":{"issue":"1","published-print":{"date-parts":[[2026,1,5]]}},"alternative-id":["10.1002\/jcc.70299"],"URL":"https:\/\/doi.org\/10.1002\/jcc.70299","archive":["Portico"],"relation":{},"ISSN":["0192-8651","1096-987X"],"issn-type":[{"value":"0192-8651","type":"print"},{"value":"1096-987X","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,12,18]]},"assertion":[{"value":"2025-10-03","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-12-08","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-12-18","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e70299"}}