{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,16]],"date-time":"2026-01-16T19:11:17Z","timestamp":1768590677249,"version":"3.49.0"},"reference-count":57,"publisher":"Wiley","issue":"34","license":[{"start":{"date-parts":[[2015,10,22]],"date-time":"2015-10-22T00:00:00Z","timestamp":1445472000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Eur J Org Chem"],"published-print":{"date-parts":[[2015,12]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p><jats:italic>C<\/jats:italic>\u2010Amino nitrile imine has been generated as primary photoproduct (<jats:italic>\u03bb<\/jats:italic> = 220 nm) of 5\u2010amino\u20102<jats:italic>H<\/jats:italic>\u2010tetrazole isolated in an argon matrix at 15 K. Subsequent photochemical experiments (<jats:italic>\u03bb<\/jats:italic> = 330 nm) demonstrated that <jats:italic>C<\/jats:italic>\u2010amino nitrile imine isomerizes to the corresponding three\u2010membered\u2010ring 1<jats:italic>H<\/jats:italic>\u2010diazirine and decomposes to methylenimine. The experimentally observed \u03bd<jats:sub>as<\/jats:sub>(CNN) absorption at 1998 cm<jats:sup>\u20131<\/jats:sup> and a carbenic resonance structure contribution of around 20\u2009%, predicted by natural resonance theory calculations, demonstrate that the protoproduced <jats:italic>C<\/jats:italic>\u2010amino nitrile imine has significant carbenic character. These results pave the way to the discovery of carbenic nitrile imines.<\/jats:p>","DOI":"10.1002\/ejoc.201501153","type":"journal-article","created":{"date-parts":[[2015,10,23]],"date-time":"2015-10-23T08:04:10Z","timestamp":1445587450000},"page":"7484-7493","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":40,"title":["The Quest for Carbenic Nitrile Imines: Experimental and Computational Characterization of <i>C<\/i>\u2010Amino Nitrile Imine"],"prefix":"10.1002","volume":"2015","author":[{"given":"Cl\u00e1udio M.","family":"Nunes","sequence":"first","affiliation":[]},{"given":"Igor","family":"Reva","sequence":"additional","affiliation":[]},{"given":"M\u00e1rio T. S.","family":"Rosado","sequence":"additional","affiliation":[]},{"given":"Rui","family":"Fausto","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2015,10,22]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/0471221902"},{"key":"e_1_2_6_2_2","volume-title":"1,3\u2010Dipolar Cycloaddition Chemistry","year":"1984"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol303097j"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.730"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.361"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201208741"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar200021p"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja407867a"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200901220"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja803598e"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200705805"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp0480044"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja100512d"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja800009z"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00024a007"},{"key":"e_1_2_6_16_2","unstructured":"\u00a0"},{"key":"e_1_2_6_17_2","unstructured":"We recently discovered a 1 3\u2010dipolar species theC\u2010phenyl nitrile imine (Ph\u2013CNN\u2013H) that co\u2010exists in two different structures corresponding to different energy minima (see ref.[16b]);"},{"key":"e_1_2_6_18_2","first-page":"51","author":"Nunes C. M.","year":"2015","journal-title":"Chem. Commun."},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja2118442"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199405271"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00070a019"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1039\/b407302a"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1039\/b517030c"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jphotochemrev.2013.09.001"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo402744f"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.mencom.2014.06.002"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp5001804"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jphotochem.2013.12.011"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jphotochem.2012.10.023"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1002\/jlac.199619960704"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp208510d"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo402875c"},{"key":"e_1_2_6_33_2","unstructured":"B\u00e9gu\u00e9 and Wentrup have investigated theoretically different amino\u2010 hydroxy\u2010 and fluoro\u2010substituted nitrile imines and found that heteroatom substituents with a lone pair stabilize the corresponding carbenic resonance structure of nitrile imines (see ref.[30]). However the experimental study ofC\u2010fluoro nitrile imines was not possible because of the lack of synthetic methods for preparing the corresponding 5\u2010fluorotetrazoles (tetrazoles are precursors used to generate nitrile imines)."},{"key":"e_1_2_6_34_2","unstructured":"\u00a0"},{"key":"e_1_2_6_35_2","unstructured":"In agreement with what could be expected based on calculated relative energies for different tautomers of 5\u2010aminotetrazole (1) discussed in the section \u201cTautomeric Equilibria in 5\u2010Monosubstituted Tetrazoles\u201d (Table\u00a01). The 2H\u2010tautomer was also found to be the most stable form in the gas phase and the major or exclusive form deposited in the matrix in several 5\u2010monsubtituted tetrazoles such as 5\u2010methyl\u2010 5\u2010phenyl\u2010 and 5\u2010chlorotetrazole (see refs.[16 23 32b]);"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1039\/b111329c"},{"key":"e_1_2_6_37_2","unstructured":"It was observed that the photochemistry of1\u2033only occurs with irradiation with\u03bb\u2264 260 nm also in accord with the UV\/Vis spectrum of 5\u2010aminotetrazole (1; Figure S2 in the Supporting Information)."},{"key":"e_1_2_6_38_2","unstructured":"Our optical parametric oscillator with a frequency doubling option has an intrinsic blind spot in the 370\u2013340 nm region. Because of this irradiation experiments were not carried out in this frequency range."},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-2852(75)90122-8"},{"key":"e_1_2_6_40_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1734312"},{"key":"e_1_2_6_41_2","unstructured":"Scaled B3LYP\/6\u2013311++G(d p) frequencies for the HNC molecule appear at 3617 [\u03bd(NH)] 2053 [\u03bd(NC)] and 484 [\u03b4(HCN)] cm\u20131."},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00044a034"},{"key":"e_1_2_6_43_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00047a012"},{"key":"e_1_2_6_44_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature07010"},{"key":"e_1_2_6_45_2","unstructured":"These species were also selected because they were previously produced in low\u2010temperature matrices (see refs.[23 28]) and the experimental frequencies of the \u03bdas(CNN) mode could be used as complementary information on their structures."},{"key":"e_1_2_6_46_2","volume-title":"Reactive Intermediate Chemistry","author":"Bertrand G.","year":"2004"},{"key":"e_1_2_6_47_2","unstructured":"M. J. Frisch G. W. Trucks H. B. Schlegel G. E. Scuseria M. A. Robb J. R. Cheeseman G. Scalmani V. Barone B. Mennucci G. A. Petersson H. Nakatsuji M. Caricato X. Li H. P. Hratchian A. F. Izmaylov J. Bloino G. Zheng J. L. Sonnenberg M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai T. Vreven J. A. Montgomery Jr. J. E. Peralta F. Ogliaro M. Bearpark J. J. Heyd E. Brothers K. N. Kudin V. N. Staroverov R. Kobayashi J. Normand K. Raghavachari A. Rendell J. C. Burant S. S. Iyengar J. Tomasi M. Cossi N. Rega J. M. Millam M. Klene J. E. Knox J. B. Cross V. Bakken C. Adamo J. Jaramillo R. Gomperts R. E. Stratmann O. Yazyev A. J. Austin R. Cammi C. Pomelli J. W. Ochterski R. L. Martin K. Morokuma V. G. Zakrzewski G. A. Voth P. Salvador J. J. Dannenberg S. Dapprich A. D. Daniels \u00d6. Farkas J. B. Foresman J. V. Ortiz J. Cioslowski D. J. Fox Gaussian 09 revision D.01 Gaussian Inc. Wallingford CT 2009."},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.540141112"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo301699z"},{"key":"e_1_2_6_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja207717k"},{"key":"e_1_2_6_51_2","unstructured":"K. K. Irikura Program SYNSPEC National Institute of Standards and Technology Gaithersburg MD 20899 USA 1995."},{"key":"e_1_2_6_52_2","unstructured":"E. D. Glendening J. K. Badenhoop A. E. Reed J. E. Carpenter J. A. Bohmann C. M. Morales F. Weinhold NBO 5.0 Theoretical Chemistry Institute University of Wisconsin Madison WI 2001."},{"key":"e_1_2_6_53_2","doi-asserted-by":"publisher","DOI":"10.1017\/CBO9780511614569"},{"key":"e_1_2_6_54_2","volume-title":"The Nature of the Chemical Bond and the Structure of Molecules and Crystals: An Introduction to Modern Structural Chemistry","author":"Pauling L.","year":"1960"},{"key":"e_1_2_6_55_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1096-987X(19980430)19:6<593::AID-JCC3>3.0.CO;2-M"},{"key":"e_1_2_6_56_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1096-987X(19980430)19:6<610::AID-JCC4>3.0.CO;2-U"},{"key":"e_1_2_6_57_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1096-987X(19980430)19:6<628::AID-JCC5>3.0.CO;2-T"}],"container-title":["European Journal of Organic Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fejoc.201501153","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/ejoc.201501153","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,15]],"date-time":"2025-10-15T10:49:39Z","timestamp":1760525379000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/ejoc.201501153"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2015,10,22]]},"references-count":57,"journal-issue":{"issue":"34","published-print":{"date-parts":[[2015,12]]}},"alternative-id":["10.1002\/ejoc.201501153"],"URL":"https:\/\/doi.org\/10.1002\/ejoc.201501153","archive":["Portico"],"relation":{},"ISSN":["1434-193X","1099-0690"],"issn-type":[{"value":"1434-193X","type":"print"},{"value":"1099-0690","type":"electronic"}],"subject":[],"published":{"date-parts":[[2015,10,22]]},"assertion":[{"value":"2015-09-04","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2015-10-22","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}