{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,30]],"date-time":"2026-04-30T21:55:30Z","timestamp":1777586130937,"version":"3.51.4"},"reference-count":28,"publisher":"SAGE Publications","issue":"3","license":[{"start":{"date-parts":[[2020,1,22]],"date-time":"2020-01-22T00:00:00Z","timestamp":1579651200000},"content-version":"tdm","delay-in-days":0,"URL":"https:\/\/journals.sagepub.com\/page\/policies\/text-and-data-mining-license"}],"content-domain":{"domain":["journals.sagepub.com"],"crossmark-restriction":true},"short-container-title":["Eur J Mass Spectrom (Chichester)"],"published-print":{"date-parts":[[2020,6]]},"abstract":"<jats:p>\n                    The question of whether [CH\n                    <jats:sub>2<\/jats:sub>\n                    OH]\n                    <jats:sup>+<\/jats:sup>\n                    should be described as the hydroxymethyl cation,\n                    <jats:sup>+<\/jats:sup>\n                    CH\n                    <jats:sub>2<\/jats:sub>\n                    OH, or protonated formaldehyde, CH\n                    <jats:sub>2<\/jats:sub>\n                    =OH\n                    <jats:sup>+<\/jats:sup>\n                    , is reconsidered in the light of experimental information and new computational evidence. Previous arguments that the charge distribution in [CH\n                    <jats:sub>2<\/jats:sub>\n                    OH]\n                    <jats:sup>+<\/jats:sup>\n                    may be probed by considering the incremental stabilisation of [CH\n                    <jats:sub>2<\/jats:sub>\n                    OH]\n                    <jats:sup>+<\/jats:sup>\n                    induced by homologation on carbon (to give [CH\n                    <jats:sub>3<\/jats:sub>\n                    CHOH]\n                    <jats:sup>+<\/jats:sup>\n                    ) or oxygen (to produce [CH\n                    <jats:sub>2<\/jats:sub>\n                    OCH\n                    <jats:sub>3<\/jats:sub>\n                    ]\n                    <jats:sup>+<\/jats:sup>\n                    ) are critically examined. Cation stabilisation energies are shown to be better indicators of the nature of these oxonium ions. Further insight into the structure of larger C\n                    <jats:sub>n<\/jats:sub>\n                    H\n                    <jats:sub>2n+1<\/jats:sub>\n                    O\n                    <jats:sup>+<\/jats:sup>\n                    oxonium ions is obtained by considering the site of protonation of enol ethers and related species. Computational information, including AIM (Atoms and Molecules) and NBA (Natural Bond Analysis) charges on the carbon and oxygen atoms in [CH\n                    <jats:sub>2<\/jats:sub>\n                    OH]\n                    <jats:sup>+<\/jats:sup>\n                    and related species, is considered critically. Particular attention is focused on the calculated bond lengths and barriers to rotation about the C\u2013O bond(s) in [CH\n                    <jats:sub>2<\/jats:sub>\n                    OH]\n                    <jats:sup>+<\/jats:sup>\n                    , [CH\n                    <jats:sub>3<\/jats:sub>\n                    CHOH]\n                    <jats:sup>+<\/jats:sup>\n                    , [(CH\n                    <jats:sub>3<\/jats:sub>\n                    )\n                    <jats:sub>2<\/jats:sub>\n                    COH]\n                    <jats:sup>+<\/jats:sup>\n                    , CH\n                    <jats:sub>3<\/jats:sub>\n                    OH and [CH\n                    <jats:sub>2<\/jats:sub>\n                    OCH\n                    <jats:sub>3<\/jats:sub>\n                    ]\n                    <jats:sup>+<\/jats:sup>\n                    and the C\u2013N bond in [CH\n                    <jats:sub>2<\/jats:sub>\n                    NH\n                    <jats:sub>2<\/jats:sub>\n                    ]\n                    <jats:sup>+<\/jats:sup>\n                    . Trends in these data are consistent with appreciable \u03c0-bonding only in the C\u2013O connections which correspond to the C=O bond in the parent aldehyde or ketone from which the oxonium ion may be considered to be derived by protonation or alkyl cationation.\n                  <\/jats:p>","DOI":"10.1177\/1469066719894969","type":"journal-article","created":{"date-parts":[[2020,1,22]],"date-time":"2020-01-22T23:49:35Z","timestamp":1579736975000},"page":"187-194","update-policy":"https:\/\/doi.org\/10.1177\/sage-journals-update-policy","source":"Crossref","is-referenced-by-count":2,"title":["Experimental and computational evidence for C=O \u03c0-bonding in [CH\n                    <sub>2<\/sub>\n                    OH]\n                    <sup>+<\/sup>\n                    and related oxonium ions"],"prefix":"10.1177","volume":"26","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1555-7034","authenticated-orcid":false,"given":"Richard D","family":"Bowen","sequence":"first","affiliation":[{"name":"School of Chemistry and Biosciences, Faculty of Life Sciences, University of Bradford, Bradford, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"William HC","family":"Martin","sequence":"additional","affiliation":[{"name":"School of Chemistry and Biosciences, Faculty of Life Sciences, University of Bradford, Bradford, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Charles E","family":"Hudson","sequence":"additional","affiliation":[{"name":"Department of Neuroscience and Cell Biology, University of Texas Medical Branch, 301 University Boulevard, Galveston, TX, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"David J","family":"McAdoo","sequence":"additional","affiliation":[{"name":"Department of Neuroscience and Cell Biology, University of Texas Medical Branch, 301 University Boulevard, Galveston, TX, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"179","published-online":{"date-parts":[[2020,1,22]]},"reference":[{"key":"bibr1-1469066719894969","unstructured":"Patai S (ed.). Chemistry of the carbonyl group. New York: Interscience, 1966."},{"key":"bibr2-1469066719894969","volume-title":"Interpretation of mass spectra","author":"McLafferty FW","year":"1993","edition":"4"},{"key":"bibr3-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1021\/cr60051a003"},{"key":"bibr4-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1002\/oms.1210281234"},{"key":"bibr5-1469066719894969","unstructured":"Clayden JP, Greeves N, Warren S, et\u00a0al. Organic chemistry.  Oxford:  Oxford University Press, 2003, p. 410."},{"key":"bibr6-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1021\/ja00465a022"},{"key":"bibr7-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1016\/S1044-0305(99)00004-5"},{"key":"bibr8-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1021\/ol025570d"},{"key":"bibr9-1469066719894969","doi-asserted-by":"crossref","first-page":"705","DOI":"10.1039\/b209955c","volume":"1","author":"Bache-Andreasson L","year":"2003","journal-title":"Org Biomol Chem"},{"key":"bibr10-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1063\/1.1756132"},{"key":"bibr11-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1002\/hlca.200490248"},{"key":"bibr12-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2006.02.161"},{"key":"bibr13-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1139\/v82-338"},{"key":"bibr14-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1021\/ja00335a008"},{"key":"bibr15-1469066719894969","doi-asserted-by":"crossref","unstructured":"Lias SG, Liebman JF, Levin RD,\n                      J Phys Chem Ref Data\n                      1984; 13, 695; Suppl. 1.","DOI":"10.1063\/1.555719"},{"key":"bibr16-1469066719894969","unstructured":"Lias SG, Bartmess JE, Liebman JF, Holmes JL, Levin RD and Mallard WG,\n                      J Phys Chem Ref Data\n                      1988; 17, Suppl 1."},{"key":"bibr17-1469066719894969","doi-asserted-by":"crossref","unstructured":"Hunter EPL and Lias SG.\n                      J Phys Chem Ref Data\n                      1998; 27, 413.","DOI":"10.1063\/1.556018"},{"key":"bibr18-1469066719894969","unstructured":"http:\/\/webbook.nist.gov."},{"key":"bibr19-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1139\/v81-322"},{"key":"bibr20-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1002\/mas.1280100304"},{"key":"bibr21-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1021\/ja00950a014"},{"key":"bibr22-1469066719894969","unstructured":"Frisch MJ, Trucks GW, Schlegel HB, et\u00a0al. Gaussian Int, Pittsburgh, PA (1998); see also, NBA Version 3.1, Glendening ED, Reed AE, Carpenter JE and Weinhold F."},{"key":"bibr23-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1063\/1.449486"},{"key":"bibr24-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1002\/mas.1280070402"},{"key":"bibr25-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1021\/ar00012a002"},{"key":"bibr26-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1021\/ar00030a001"},{"key":"bibr27-1469066719894969","volume-title":"Theoretical chemistry institute","author":"Glendening ED","year":"1996"},{"key":"bibr28-1469066719894969","doi-asserted-by":"publisher","DOI":"10.1021\/ar990069f"}],"container-title":["European Journal of Mass Spectrometry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/journals.sagepub.com\/doi\/pdf\/10.1177\/1469066719894969","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/journals.sagepub.com\/doi\/full-xml\/10.1177\/1469066719894969","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/journals.sagepub.com\/doi\/pdf\/10.1177\/1469066719894969","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,4,28]],"date-time":"2026-04-28T20:04:23Z","timestamp":1777406663000},"score":1,"resource":{"primary":{"URL":"https:\/\/journals.sagepub.com\/doi\/10.1177\/1469066719894969"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,1,22]]},"references-count":28,"journal-issue":{"issue":"3","published-print":{"date-parts":[[2020,6]]}},"alternative-id":["10.1177\/1469066719894969"],"URL":"https:\/\/doi.org\/10.1177\/1469066719894969","relation":{},"ISSN":["1469-0667","1751-6838"],"issn-type":[{"value":"1469-0667","type":"print"},{"value":"1751-6838","type":"electronic"}],"subject":[],"published":{"date-parts":[[2020,1,22]]}}}