{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,26]],"date-time":"2026-02-26T15:03:35Z","timestamp":1772118215825,"version":"3.50.1"},"reference-count":44,"publisher":"Wiley","issue":"1","license":[{"start":{"date-parts":[[2024,11,13]],"date-time":"2024-11-13T00:00:00Z","timestamp":1731456000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemistryEurope"],"published-print":{"date-parts":[[2025,1]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    Controlling QMT reactivity remains exceptionally challenging and largely unexplored, as it requires rationales distinctly different from those used for classical chemical reactivity. Herein, we investigated how QMT reactivity can be controlled using electronic substituent effects. Benzazirines, which have the exceptional feature to react via two competitive QMT pathways, were used as model compounds. Three novel derivatives with increasingly stronger electron\u2010donating substituents at C4 [R = OH, N(CH\n                    <jats:sub>3<\/jats:sub>\n                    )\n                    <jats:sub>2<\/jats:sub>\n                    , and N(CH\n                    <jats:sub>2<\/jats:sub>\n                    )\n                    <jats:sub>4<\/jats:sub>\n                    ] were generated in argon matrices at 3\u2005K. Remarkably, different QMT selectivities were observed in all benzazirines. As the electron\u2010donating strength of the substituent increases, the QMT ring\u2010opening to nitrene starts to compete with the QMT ring\u2010expansion to ketenimine, becoming the dominant process for the strongest electron\u2010donating substituent [N(CH\n                    <jats:sub>2<\/jats:sub>\n                    )\n                    <jats:sub>4<\/jats:sub>\n                    ]. A theoretical analysis of the substituent effects on the QMT reactivity of benzazirines was performed and compared with the experimental data for these and other C4 derivatives. Overall, the results compellingly demonstrate how subtle changes in electronic effects can be used to fine\u2010tune QMT selectivity.\n                  <\/jats:p>","DOI":"10.1002\/ceur.202400060","type":"journal-article","created":{"date-parts":[[2024,11,14]],"date-time":"2024-11-14T01:05:31Z","timestamp":1731546331000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Competitive Heavy\u2010Atom Tunneling Reactions Controlled Through Electronic Effects"],"prefix":"10.1002","volume":"3","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\/0000-0002-3371-1031","authenticated-orcid":false,"given":"Fumito","family":"Saito","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry Justus Liebig University  Heinrich-Buff-Ring 17 35392 Giessen Germany"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7734-6427","authenticated-orcid":false,"given":"Bastian","family":"Bernhardt","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"}]},{"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"}]}],"member":"311","published-online":{"date-parts":[[2024,11,13]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1749610"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/tf9353100875"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1039\/tf9363201333"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1098\/rspa.1936.0060"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01607a027"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1203761"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b06035"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja012205t"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c04329"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0SC06295B"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.2c00151"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b04593"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsomega.1c07176"},{"key":"e_1_2_7_14_1","unstructured":"F.\u2005A. Carey R.\u2005J. Sundberg Advanced Organic Chemistry Part A: Structure and Mechanisms 5th ed.; Springer: New York 2007; pp 335\u2013344."},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscentsci.3c00926"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202001202"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja107531y"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201511028"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr400400p"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00846a073"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/wcms.1235"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201914943"},{"key":"e_1_2_7_23_1","doi-asserted-by":"crossref","unstructured":"C.\u2005M. Nunes I. Reva R. Fausto Direct Observation of Tunnelling Reactions by Matrix Isolation Spectroscopy. InTunnelling in Molecules: Nuclear Quantum Effects from Bio to Physical Chemistry; J. K\u00e4stner S. Kozuch Eds. The Royal Society of Chemistry 2021; pp 1\u201360.","DOI":"10.1039\/9781839160370-00001"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1CS01026C"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja404172s"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.9b02482"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b10495"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b06869"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202202306"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.3c00484"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CP02080H"},{"key":"e_1_2_7_32_1","doi-asserted-by":"crossref","unstructured":"H. Amlani A. Frenklah S. Kozuch Tunnelling Instability in Molecular Systems. An Exercise in Computational Chemistry Prediction Power. InTunnelling in Molecules: Nuclear Quantum Effects from Bio to Physical Chemistry; J. K\u00e4stner S. Kozuch Eds. The Royal Society of Chemistry 2021; pp 61\u201387.","DOI":"10.1039\/9781839160370-00061"},{"key":"e_1_2_7_33_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00171a038"},{"key":"e_1_2_7_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.5b01263"},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja9635241"},{"key":"e_1_2_7_36_1","doi-asserted-by":"publisher","DOI":"10.1002\/qua.1518"},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr00002a004"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr040055"},{"key":"e_1_2_7_39_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.25711"},{"key":"e_1_2_7_40_1","unstructured":"The width of a potential energy barrier relevant for QMT was obtained as the distance between the two classical turning points (see more details in section 2.3 and Table\u2005S13 of the SI). Those are defined as the points where the total energy of the system is equal to the potential i.\u2009e. the points where the energy at the vibrational ground state of the reactant intersects the potential energy surface."},{"key":"e_1_2_7_41_1","unstructured":"Structure3f\u2032is a minimum at the B3LYP\/6-311+G(2d p) level but has a small imaginary frequency (34icm\u22121) at the CASSCF(8 8)\/6-311+G(2d p) level. Therefore the IRC describing the3f\u2032\u219212f\u2032reaction computed at the CASSCF(8 8) had to be truncated at a geometry similar to3f\u2032. Thus the3f\u2032\u219212f\u2032QMT computed rate is a rough estimation."},{"key":"e_1_2_7_42_1","unstructured":"QMT reactivity also depends on the shape of the PES of a reaction. Actually the one-dimensional barrier width may not be a completely reliable indicator for QMT reactivity. These two points are well illustrated in section 4 of the SI. A more precise indicator for QMT reactivity might be the area of the permeation barrier."},{"key":"e_1_2_7_43_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.abq8663"},{"key":"e_1_2_7_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b02272"}],"container-title":["ChemistryEurope"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/ceur.202400060","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T20:19:53Z","timestamp":1760300393000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/ceur.202400060"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,11,13]]},"references-count":44,"journal-issue":{"issue":"1","published-print":{"date-parts":[[2025,1]]}},"alternative-id":["10.1002\/ceur.202400060"],"URL":"https:\/\/doi.org\/10.1002\/ceur.202400060","archive":["Portico"],"relation":{"has-preprint":[{"id-type":"doi","id":"10.26434\/chemrxiv-2024-d0l0z","asserted-by":"object"}]},"ISSN":["2751-4765","2751-4765"],"issn-type":[{"value":"2751-4765","type":"print"},{"value":"2751-4765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,11,13]]},"assertion":[{"value":"2024-11-13","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202400060"}}