{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,17]],"date-time":"2025-10-17T00:36:33Z","timestamp":1760661393469,"version":"build-2065373602"},"reference-count":31,"publisher":"Wiley","issue":"6","license":[{"start":{"date-parts":[[2024,5,21]],"date-time":"2024-05-21T00:00:00Z","timestamp":1716249600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100000038","name":"Natural Sciences and Engineering Research Council of Canada","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100000038","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["analyticalsciencejournals.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["J Mass Spectrom"],"published-print":{"date-parts":[[2024,6]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Chloroformates are prevalent in the atmosphere due to their utilization as fuel additives and industrial solvents. These species may undergo interactions with atmospheric water resulting in protonated chloroformates. This study delves into the gas\u2010phase dissociation of these protonated species. Tandem mass spectrometry was employed to scrutinize the unimolecular dissociation of protonated methyl (<jats:bold>1<\/jats:bold>), ethyl (<jats:bold>2<\/jats:bold>), neopentyl (<jats:bold>3<\/jats:bold>), and phenyl chloroformate (<jats:bold>4<\/jats:bold>). Notably, <jats:bold>1<\/jats:bold> and <jats:bold>4<\/jats:bold> exhibited HCl loss, yielding CH<jats:sub>3<\/jats:sub>OCO<jats:sup>+<\/jats:sup> and C<jats:sub>6<\/jats:sub>H<jats:sub>5<\/jats:sub>OCO<jats:sup>+<\/jats:sup>, respectively, with <jats:bold>1<\/jats:bold> additionally generating neutral methanol and ClCO<jats:sup>+<\/jats:sup>. <jats:bold>4<\/jats:bold> additionally loses CO and CO<jats:sub>2<\/jats:sub>. In contrast, <jats:bold>2<\/jats:bold> and <jats:bold>3<\/jats:bold> each only exhibit a single fragmentation channel, with <jats:bold>2<\/jats:bold> losing C<jats:sub>2<\/jats:sub>H<jats:sub>4<\/jats:sub> to generate protonated chloroformic acid and <jats:bold>3<\/jats:bold> generating protonated 2\u2010methylbutene by losing neutral chloroformic acid. Density functional theory at the B3LYP\/6\u2010311+G(d,p) level of theory was employed to explore minimum energy reaction pathways for each ion, and CBS\u2010QB3 single\u2010point energy calculations were added to provide reliable energetics. The Rice\u2013Ramsperger\u2013Kassel\u2013Marcus (RRKM) calculations of the rate constants for selected competing processes were carried out to link theory and experiment. One common unimolecular process observed was the 1,3\u2010H shift of the proton from the carbonyl oxygen to the ester oxygen before dissociation.<\/jats:p>","DOI":"10.1002\/jms.5044","type":"journal-article","created":{"date-parts":[[2024,5,21]],"date-time":"2024-05-21T03:39:21Z","timestamp":1716262761000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["On the fate of protonated chloroformates in the gas phase: a competition between forming HCl and chloroformic acid"],"prefix":"10.1002","volume":"59","author":[{"given":"Malick","family":"Diedhiou","sequence":"first","affiliation":[{"name":"Department of Chemistry and Biomolecular Sciences University of Ottawa  Ottawa K1N 6N5 Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6112-4398","authenticated-orcid":false,"given":"Paul M.","family":"Mayer","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biomolecular Sciences University of Ottawa  Ottawa K1N 6N5 Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,5,21]]},"reference":[{"key":"e_1_2_10_2_1","doi-asserted-by":"publisher","DOI":"10.3390\/molecules26175278"},{"key":"e_1_2_10_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.est.5b05105"},{"key":"e_1_2_10_4_1","doi-asserted-by":"publisher","DOI":"10.3390\/ijerph182413147"},{"key":"e_1_2_10_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp0041398"},{"key":"e_1_2_10_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/cphc.200900387"},{"key":"e_1_2_10_7_1","doi-asserted-by":"publisher","DOI":"10.1039\/d2ea00087c"},{"key":"e_1_2_10_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ijhydene.2011.11.077"},{"key":"e_1_2_10_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp201487u"},{"key":"e_1_2_10_10_1","doi-asserted-by":"publisher","DOI":"10.1029\/2003JD003786"},{"key":"e_1_2_10_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr60232a004"},{"key":"e_1_2_10_12_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040\u20104020(02)01331\u20105"},{"key":"e_1_2_10_13_1","doi-asserted-by":"publisher","DOI":"10.1136\/oem.58.10.684"},{"key":"e_1_2_10_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201403441"},{"key":"e_1_2_10_15_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2013.06.026"},{"key":"e_1_2_10_16_1","doi-asserted-by":"publisher","DOI":"10.1007\/1\u20104020\u20104232\u20109_13"},{"key":"e_1_2_10_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/jasms.3c00334"},{"key":"e_1_2_10_18_1","doi-asserted-by":"publisher","DOI":"10.1080\/00304940409355972"},{"key":"e_1_2_10_19_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.atmosenv.2007.12.057"},{"key":"e_1_2_10_20_1","doi-asserted-by":"publisher","DOI":"10.1177\/07482337231172811"},{"key":"e_1_2_10_21_1","doi-asserted-by":"publisher","DOI":"10.3390\/molecules28114431"},{"key":"e_1_2_10_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/jms.5004"},{"key":"e_1_2_10_23_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.comptc.2023.114323"},{"volume-title":"Metastable Ions","year":"1973","author":"Cooks RG","key":"e_1_2_10_24_1"},{"key":"e_1_2_10_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp9919617"},{"key":"e_1_2_10_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp3091705"},{"key":"e_1_2_10_27_1","unstructured":"FrischMJ TrucksGW SchlegelHB ScuseriaGE RobbMA CheesemanJR ScalmaniG BaroneV PeterssonGA NakatsujiH LiX CaricatoM MarenichAV BloinoJ JaneskoBG GompertsR MennucciB HratchianHP OrtizJV IzmaylovAF SonnenbergJL WilliamsD DingF LippariniF EgidiF GoingsJ PengB PetroneA HendersonT RanasingheD ZakrzewskiVG GaoJ RegaN ZhengG LiangW HadaM EharaM ToyotaK FukudaR HasegawaJ IshidaM NakajimaT HondaY KitaoO NakaiH VrevenT ThrossellK MontgomeryJr.JA PeraltaJE OgliaroF BearparkMJ HeydJJ BrothersEN KudinKN StaroverovVN KeithTA KobayashiR NormandJ RaghavachariK RendellAP BurantJC IyengarSS TomasiJ CossiM MillamJM KleneM AdamoC CammiR OchterskiJW MartinRL MorokumaK FarkasO ForesmanJB FoxDJ.Gaussian 16 rev. B.01.2016."},{"key":"e_1_2_10_28_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.464913"},{"key":"e_1_2_10_29_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.37.785"},{"key":"e_1_2_10_30_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.477924"},{"key":"e_1_2_10_31_1","doi-asserted-by":"publisher","DOI":"10.1016\/S1044-0305(96)00212-7"},{"key":"e_1_2_10_32_1","doi-asserted-by":"publisher","DOI":"10.1093\/oso\/9780195074949.001.0001"}],"container-title":["Journal of Mass Spectrometry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/analyticalsciencejournals.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/jms.5044","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,16]],"date-time":"2025-10-16T19:10:17Z","timestamp":1760641817000},"score":1,"resource":{"primary":{"URL":"https:\/\/analyticalsciencejournals.onlinelibrary.wiley.com\/doi\/10.1002\/jms.5044"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,5,21]]},"references-count":31,"journal-issue":{"issue":"6","published-print":{"date-parts":[[2024,6]]}},"alternative-id":["10.1002\/jms.5044"],"URL":"https:\/\/doi.org\/10.1002\/jms.5044","archive":["Portico"],"relation":{},"ISSN":["1076-5174","1096-9888"],"issn-type":[{"type":"print","value":"1076-5174"},{"type":"electronic","value":"1096-9888"}],"subject":[],"published":{"date-parts":[[2024,5,21]]},"assertion":[{"value":"2024-02-20","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2024-05-06","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2024-05-21","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e5044"}}