{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,27]],"date-time":"2026-04-27T20:27:04Z","timestamp":1777321624115,"version":"3.51.4"},"reference-count":62,"publisher":"Wiley","issue":"39","license":[{"start":{"date-parts":[[2024,5,24]],"date-time":"2024-05-24T00:00:00Z","timestamp":1716508800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100010663","name":"H2020 European Research Council","doi-asserted-by":"publisher","award":["101054751 \"COLDOC\""],"award-info":[{"award-number":["101054751 \"COLDOC\""]}],"id":[{"id":"10.13039\/100010663","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":[[2024,7,11]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    Probing quantum mechanical tunneling (QMT) in chemical reactions is crucial to understanding and developing new transformations. Primary H\/D kinetic isotopic effects (KIEs) beyond the semiclassical maximum values of 7\u201310 (room temperature) are commonly used to assess substantial QMT contributions in one\u2010step hydrogen transfer reactions, because of the much greater QMT probability of protium vs. deuterium. Nevertheless, we report here the discovery of a reaction model occurring exclusively by H\u2010atom QMT with residual primary H\/D KIEs. 2\u2010Hydroxyphenylnitrene, generated in N\n                    <jats:sub>2<\/jats:sub>\n                    matrix, was found to isomerize to an imino\u2010ketone via sequential (domino) QMT involving\n                    <jats:italic>anti<\/jats:italic>\n                    to\n                    <jats:italic>syn<\/jats:italic>\n                    OH\u2010rotamerization (rate determining step) and [1,4]\u2010H shift reactions. These sequential QMT transformations were also observed in the OD\u2010deuterated sample, and unexpected primary H\/D KIEs between 3 and 4 were measured at 3 to 20\u2005K. Analogous residual primary H\/D KIEs were found in the\n                    <jats:italic>anti<\/jats:italic>\n                    to\n                    <jats:italic>syn<\/jats:italic>\n                    OH\u2010rotamerization QMT of 2\u2010cyanophenol in a N\n                    <jats:sub>2<\/jats:sub>\n                    matrix. Evidence strongly indicates that these intriguing isotope\u2010insensitive QMT reactivities arise due to the solvation effects of the N\n                    <jats:sub>2<\/jats:sub>\n                    matrix medium, putatively through coupling with the moving H\/D tunneling particle. Should a similar scenario be extrapolated to conventional solution conditions, then QMT may have been overlooked in many chemical reactions.\n                  <\/jats:p>","DOI":"10.1002\/chem.202401323","type":"journal-article","created":{"date-parts":[[2024,5,6]],"date-time":"2024-05-06T08:54:05Z","timestamp":1714985645000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["Hydrogen Tunneling Exhibiting Unexpectedly Small Primary Kinetic Isotope Effects"],"prefix":"10.1002","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7845-9415","authenticated-orcid":false,"given":"Jos\u00e9 P. L.","family":"Roque","sequence":"first","affiliation":[{"name":"University of Coimbra, CQC-IMS Department of Chemistry  3004-535 Coimbra Portugal"},{"name":"Institute of Organic Chemistry Justus Liebig University  Heinrich-Buff-Ring 17 35392 Giessen Germany"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8511-1230","authenticated-orcid":false,"given":"Cl\u00e1udio M.","family":"Nunes","sequence":"additional","affiliation":[{"name":"University of Coimbra, CQC-IMS Department of Chemistry  3004-535 Coimbra Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3608-5515","authenticated-orcid":false,"given":"Peter R.","family":"Schreiner","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry Justus Liebig University  Heinrich-Buff-Ring 17 35392 Giessen Germany"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8264-6854","authenticated-orcid":false,"given":"Rui","family":"Fausto","sequence":"additional","affiliation":[{"name":"University of Coimbra, CQC-IMS Department of Chemistry  3004-535 Coimbra Portugal"},{"name":"Faculty Sciences and Letters Department of Physics Istanbul Kultur University, Bakirkoy  Istanbul 34158 Turkey"}]}],"member":"311","published-online":{"date-parts":[[2024,5,24]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-1-4899-2891-7"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00517a004"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100464a026"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1203761"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b06035"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201705140"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b06869"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c09026"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b02272"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja509465w"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1146\/annurev-biochem-051710-133623"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr1001035"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.8b00226"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-021-23988-y"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.202300962"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2DT01529C"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/poc.1676"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr60211a004"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.abq8663"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CC05214K"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5DT00809C"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1246\/cl.1998.549"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja4123076"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202102189"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00519a021"},{"key":"e_1_2_7_26_1","unstructured":"Hama et\u2005al. also claim a QMT reaction with residual primary H\/D KIEs the addition of protium and deuterium atoms to benzene at cryogenic temperatures. However in this case the process of H\/D surface diffusion is the rate-determining step and not the QMT reaction. See ref. 49."},{"key":"e_1_2_7_27_1","first-page":"1","volume-title":"Tunnelling in Molecules: Nuclear Quantum Effects from Bio to Physical Chemistry","author":"Nunes C. M.","year":"2021"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202201775"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202309717"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.trechm.2020.08.006"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1SC02853G"},{"key":"e_1_2_7_32_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1CS01026C"},{"key":"e_1_2_7_33_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c04329"},{"key":"e_1_2_7_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00236a047"},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja961827p"},{"key":"e_1_2_7_36_1","unstructured":"A fresh sample ofd-32aat 10\u2005K was left continuously exposed to IR light below 2200\u2005cm\u22121for 2\u2005h more than the total exposure during the kinetic measurements and a decay \u22643\u2009% was observed (due to QMT). This clearly indicates that IR light below 2200\u2005cm\u22121has a negligible effect on the decay ofd-32a."},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b03322"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202102010"},{"key":"e_1_2_7_39_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3484943"},{"key":"e_1_2_7_40_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cplett.2019.137069"},{"key":"e_1_2_7_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.9b01382"},{"key":"e_1_2_7_42_1","unstructured":"In the kinetic decay of4aandd-4a the measurements were conducted during a time period where the sample amount decreases towards a plateau. The sample amount plateau was determined by leaving the sample in the dark for a much longer period and this was assumed for simplification purposes to correspond to the total decay of the sample. More details are given in the \u201cKinetics\u201d section of the SI."},{"key":"e_1_2_7_43_1","doi-asserted-by":"publisher","DOI":"10.1002\/9780470116449.ch3"},{"key":"e_1_2_7_44_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.479055"},{"key":"e_1_2_7_45_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4754435"},{"key":"e_1_2_7_46_1","doi-asserted-by":"publisher","DOI":"10.3390\/molecules27238248"},{"key":"e_1_2_7_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b02605"},{"key":"e_1_2_7_48_1","doi-asserted-by":"publisher","DOI":"10.1002\/poc.1663"},{"key":"e_1_2_7_49_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.1501328112"},{"key":"e_1_2_7_50_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.2c00151"},{"key":"e_1_2_7_51_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41586-022-05451-0"},{"key":"e_1_2_7_52_1","doi-asserted-by":"publisher","DOI":"10.1002\/ntls.20230006"},{"key":"e_1_2_7_53_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1521429"},{"key":"e_1_2_7_54_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3115642"},{"key":"e_1_2_7_55_1","unstructured":"A case could be made for the observation of H\/D-atom QMT reactions with significant primary H\/D KIE for molecules coupled to the N2matrix. Such a scenario must be observed if the motion of the H\/D-atom determines the QMT rate because this process is isotope-sensitive. At this stage it is not obvious how to predict the occurrence of the scenario detailed in the text (rate determined mainly by the medium motion) or the above-mentioned alternative (rate determined mainly by H\/D-atom motion)."},{"key":"e_1_2_7_56_1","unstructured":"Investigations of QMT rates in light14N2vs heavy15N2isotopic matrices were limited to the reaction of4afor the reason provided in the \u201cKinetic\u201d section in the SI."},{"key":"e_1_2_7_57_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-020-18595-2"},{"key":"e_1_2_7_58_1","unstructured":"Caldin et\u2005al. described in the 1970s that the abstraction of a proton from 4\u2013nitrophenylnitromethane by strong bases occurs with tunneling contributions in which the primary H\/D KIEs decrease significatively upon increasing the polarity of the solvent. Likewise they suggest that the motion of medium molecules should be coupled with the motion of the proton in the more polar solvents (refs. 59 60). However latter reinvestigations showed that the measured KIEs were erroneous due to unrecognized loss of the isotopic label (refs. 61 62)."},{"key":"e_1_2_7_59_1","doi-asserted-by":"publisher","DOI":"10.1039\/f19757101876"},{"key":"e_1_2_7_60_1","doi-asserted-by":"publisher","DOI":"10.1039\/c39730000854"},{"key":"e_1_2_7_61_1","doi-asserted-by":"publisher","DOI":"10.1002\/poc.610030111"},{"key":"e_1_2_7_62_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00391a044"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202401323","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T19:45:58Z","timestamp":1760298358000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.202401323"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,5,24]]},"references-count":62,"journal-issue":{"issue":"39","published-print":{"date-parts":[[2024,7,11]]}},"alternative-id":["10.1002\/chem.202401323"],"URL":"https:\/\/doi.org\/10.1002\/chem.202401323","archive":["Portico"],"relation":{"has-preprint":[{"id-type":"doi","id":"10.26434\/chemrxiv-2023-8h22d-v2","asserted-by":"object"},{"id-type":"doi","id":"10.26434\/chemrxiv-2023-8h22d","asserted-by":"object"}]},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,5,24]]},"assertion":[{"value":"2024-04-03","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2024-05-24","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202401323"}}