{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,15]],"date-time":"2026-06-15T22:21:41Z","timestamp":1781562101332,"version":"3.54.5"},"reference-count":70,"publisher":"Wiley","issue":"69","license":[{"start":{"date-parts":[[2018,9,26]],"date-time":"2018-09-26T00:00:00Z","timestamp":1537920000000},"content-version":"am","delay-in-days":314,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#am"},{"start":{"date-parts":[[2017,11,16]],"date-time":"2017-11-16T00:00:00Z","timestamp":1510790400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100006132","name":"Office of Science","doi-asserted-by":"publisher","award":["Catalysis Center Program"],"award-info":[{"award-number":["Catalysis Center Program"]}],"id":[{"id":"10.13039\/100006132","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2017,12,11]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The hydrogenation energies and singlet\u2013triplet (S\u2013T) splittings at the G3MP2 level of theory have been calculated for a wide range of carbenes. The carbene, :CXY with different substituents (X,\u2009Y=H, CN, NC, F, Cl, OH, OCH<jats:sub>3<\/jats:sub>, CH<jats:sub>3<\/jats:sub>, CF<jats:sub>3<\/jats:sub>, SiH<jats:sub>3<\/jats:sub>, SiMe<jats:sub>3<\/jats:sub>, phenyl, CH=O, PH<jats:sub>2<\/jats:sub>, and NH<jats:sub>2<\/jats:sub>) at the carbenic carbon center, immidazole\u2010based carbenes, Bertrand's carbenes, and Seppelt's CF<jats:sub>3<\/jats:sub>CSF<jats:sub>3<\/jats:sub> were studied. The stable carbenes are singlets with large S\u2013T splittings and with the least exothermic hydrogenation energies. The singlet ground state immidazole\u2010based carbenes are calculated to have the least exothermic hydrogenation energies (\u221215 to \u221230\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>) and the largest S\u2013T gaps. The singlet ground states of the Bertrand carbenes have more exothermic hydrogenation (ca. \u221267\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>) energies and much smaller S\u2013T gaps. The more exothermic reaction energies arise due to the need to make the phosphorus planar in the carbene so that it can donate into the empty p\u2010orbital at the carbene carbon center. The bending potential at the carbene carbon center in the Bertrand compounds is very flat with a large XC:Y angle. Seppelt's CF<jats:sub>3<\/jats:sub>CSF<jats:sub>3<\/jats:sub> appears to be energetically similar to the Bertrand system, probably due to the required adjustments for geometric distortions at the sulfur center.<\/jats:p>","DOI":"10.1002\/chem.201703539","type":"journal-article","created":{"date-parts":[[2017,9,26]],"date-time":"2017-09-26T10:37:04Z","timestamp":1506422224000},"page":"17556-17565","source":"Crossref","is-referenced-by-count":16,"title":["Characterization of Carbenes via Hydrogenation Energies, Stability, and Reactivity: What's in a Name?"],"prefix":"10.1002","volume":"23","author":[{"given":"Monica","family":"Vasiliu","sequence":"first","affiliation":[{"name":"Department of Chemistry The University of Alabama, Shelby Hall  Tuscaloosa Alabama 35487-0336 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4901-3235","authenticated-orcid":false,"given":"Kirk A.","family":"Peterson","sequence":"additional","affiliation":[{"name":"Department of Chemistry Washington State University  Pullman WA 99164-4630 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Anthony J.","family":"Arduengo","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Alabama, Shelby Hall  Tuscaloosa Alabama 35487-0336 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9492-0056","authenticated-orcid":false,"given":"David A.","family":"Dixon","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Alabama, Shelby Hall  Tuscaloosa Alabama 35487-0336 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2017,11,16]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr940472u"},{"key":"e_1_2_8_2_1","first-page":"171","volume-title":"Divalent Carbon","author":"Hine J. S.","year":"1964"},{"key":"e_1_2_8_3_1","unstructured":"The acronym NHC (N-tererocyclic carbene) is a subset of the class of substances addressed herein but the electronic and structural class is better captured by the grouping \u201csinglet nucleophilic carbenes\u201d (SNC) which we prefer for its succinctness and accuracy."},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00001a054"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00040a007"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar980126p"},{"key":"e_1_2_8_7_1","first-page":"151","volume-title":"N-Heterocyclic Carbenes: Effective Tools for Organometallic Synthesis","author":"\u201cSynthesis","year":"2014"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00227a028"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/om200650x"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198401501"},{"key":"e_1_2_8_10_2","first-page":"138","volume":"96","year":"1984","journal-title":"Angew. Chem."},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp055527i"},{"key":"e_1_2_8_12_1","unstructured":"S.\u2005P. Sander R.\u2005R. Friedl A.\u2005R. Ravishankara D.\u2005M. Golden C.\u2005E. Kolb M.\u2005J. Kurylo R.\u2005E. Huie V.\u2005L. Orkin M.\u2005J. Molina G.\u2005K. Moortgat B.\u2005J. Finlayson-Pitts Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies: Evaluation Number 14 JPL Publication 02\u201325 National Aeronautics and Space Administration Jet Propulsion Laboratory California Institute of Technology Pasadena California2003.http:\/\/jpldataeval.jpl.nasa.gov\/pdf\/JPL_02-25_rev02.pdf."},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp990425b"},{"key":"e_1_2_8_14_1","unstructured":"M.\u2005W. Chase \u2005Jr. NIST-JANAF Tables 4th ed. J. Phys. Chem. Ref. Data Mono. 9 Suppl. 1 (1998)."},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp202668p"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.478385"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3008061"},{"key":"e_1_2_8_18_1","first-page":"1","volume-title":"Annual Reports in Computational Chemistry, Vol. 8","author":"Dixon D. A.","year":"2012"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1007\/s00214-011-1079-5"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1080\/00268976.2012.684897"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja1071493"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja9527075"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1016\/0301-0104(80)80045-0"},{"key":"e_1_2_8_24_1","first-page":"175","volume":"14","author":"Roos B. O.","year":"1980","journal-title":"Int. J. Quantum Chem. Symp."},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.441359"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.448627"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(85)80025-7"},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.456153"},{"key":"e_1_2_8_29_1","unstructured":"H.-J. Werner P.\u2005J. Knowles G. Knizia F.\u2005R. Manby M. Sch\u00fctz P. Celani T. Korona R. Lindh A. Mitrushenkov G. Rauhut K.\u2005R. Shamasundar T.\u2005B. Adler R.\u2005D. Amos A. Bernhardsson A. Berning D.\u2005L. Cooper M.\u2005J.\u2005O. Deegan A.\u2005J. Dobbyn F. Eckert E. Goll C. Hampel A. Hesselmann G. Hetzer T. Hrenar G. Jansen C. K\u00f6ppl Y. Liu A.\u2005W. Lloyd R.\u2005A. Mata A.\u2005J. May S.\u2005J. McNicholas W. Meyer M.\u2005E. Mura A. Nicklass D.\u2005P. O\u2032Neill P. Palmieri D. Peng K. Pfl\u00fcger R. Pitzer M. Reiher T. Shiozaki H. Stoll A.\u2005J. Stone R. Tarroni T. Thorsteinsson M. Wang MOLPRO version 2012.1 a package of ab initio programs seehttp:\/\/www.molpro.net."},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1002\/wcms.82"},{"key":"e_1_2_8_31_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.23266"},{"key":"e_1_2_8_32_1","unstructured":"E.\u2005D. Glendening J.\u2005K. Badenhoop A.\u2005E. Reed J.\u2005E. Carpenter J.\u2005A. Bohmann C.\u2005M. Morales C.\u2005R. Landis F. Weinhold (Theoretical Chemistry Institute University of Wisconsin Madison WI 2013); seehttp:\/\/nbo6.chem.wisc.edu\/."},{"key":"e_1_2_8_33_1","first-page":"1792","volume-title":"Encyclopedia of Computational Chemistry, Vol. 3","author":"Weinhold F.","year":"1998"},{"key":"e_1_2_8_34_1","doi-asserted-by":"publisher","DOI":"10.1017\/CBO9780511614569"},{"key":"e_1_2_8_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr00088a005"},{"key":"e_1_2_8_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100395a015"},{"key":"e_1_2_8_37_1","volume-title":"Density Functional Theory of Atoms and Molecules","author":"Parr R. G.","year":"1989"},{"key":"e_1_2_8_38_1","doi-asserted-by":"publisher","DOI":"10.1146\/annurev.pc.46.100195.003413"},{"key":"e_1_2_8_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr990029p"},{"key":"e_1_2_8_40_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.436185"},{"key":"e_1_2_8_41_1","doi-asserted-by":"publisher","DOI":"10.1002\/3527606173"},{"key":"e_1_2_8_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00364a005"},{"key":"e_1_2_8_43_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0031-8914(34)90011-2"},{"key":"e_1_2_8_44_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.83.22.8440"},{"key":"e_1_2_8_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp053504y"},{"key":"e_1_2_8_46_1","doi-asserted-by":"publisher","DOI":"10.1039\/B605302P"},{"key":"e_1_2_8_47_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.77.3865"},{"key":"e_1_2_8_48_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.78.1396"},{"key":"e_1_2_8_49_1","doi-asserted-by":"publisher","DOI":"10.1071\/CH11246"},{"key":"e_1_2_8_50_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201408354"},{"key":"e_1_2_8_50_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201408354"},{"key":"e_1_2_8_51_1","doi-asserted-by":"publisher","DOI":"10.1021\/op500121w"},{"key":"e_1_2_8_52_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199610111"},{"key":"e_1_2_8_52_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19961080926"},{"key":"e_1_2_8_53_1","doi-asserted-by":"publisher","DOI":"10.1039\/C39930001136"},{"key":"e_1_2_8_54_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.poly.2015.07.070"},{"key":"e_1_2_8_55_1","doi-asserted-by":"publisher","DOI":"10.1039\/c1cc11737h"},{"key":"e_1_2_8_56_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja973241o"},{"key":"e_1_2_8_57_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00094a040"},{"key":"e_1_2_8_58_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00094a020"},{"key":"e_1_2_8_59_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00093a041"},{"key":"e_1_2_8_60_1","doi-asserted-by":"publisher","DOI":"10.1007\/BF00676622"},{"key":"e_1_2_8_61_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo300347k"},{"key":"e_1_2_8_62_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp0759325"},{"key":"e_1_2_8_63_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp8023292"},{"key":"e_1_2_8_64_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.464913"},{"key":"e_1_2_8_65_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.37.785"},{"key":"e_1_2_8_66_1","doi-asserted-by":"publisher","DOI":"10.1139\/v92-079"},{"key":"e_1_2_8_67_1","unstructured":"Gaussian 09 Revision E.01 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman G. Scalmani V. Barone B. Mennucci G.\u2005A. Petersson H. Nakatsuji M. Caricato X. Li H.\u2005P. Hratchian A.\u2005F. Izmaylov J. Bloino G. Zheng J.\u2005L. Sonnenberg M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai T. Vreven J.\u2005A. Montgomery\u2005Jr. J.\u2005E. Peralta F. Ogliaro M.\u2005J. Bearpark J. Heyd E.\u2005N. Brothers K.\u2005N. Kudin V.\u2005N. Staroverov R. Kobayashi J. Normand K. Raghavachari A.\u2005P. Rendell J.\u2005C. Burant S.\u2005S. Iyengar J. Tomasi M. Cossi N. Rega N.\u2005J. Millam M. Klene J.\u2005E. Knox J.\u2005B. Cross V. Bakken C. Adamo J. Jaramillo R. Gomperts R.\u2005E. Stratmann O. Yazyev A.\u2005J. Austin R. Cammi C. Pomelli J.\u2005W. Ochterski R.\u2005L. Martin K. Morokuma V.\u2005G. Zakrzewski G.\u2005A. Voth P. Salvador J.\u2005J. Dannenberg S. Dapprich A.\u2005D. Daniels \u00d6. Farkas J.\u2005B. Foresman J.\u2005V. Ortiz J. Cioslowski D.\u2005J. Fox Gaussian Inc. Wallingford CT 2009."}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201703539","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201703539","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/chem.201703539","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/am-pdf\/10.1002\/chem.201703539","content-type":"application\/pdf","content-version":"am","intended-application":"syndication"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201703539","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T11:01:23Z","timestamp":1760266883000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201703539"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2017,11,16]]},"references-count":70,"journal-issue":{"issue":"69","published-print":{"date-parts":[[2017,12,11]]}},"alternative-id":["10.1002\/chem.201703539"],"URL":"https:\/\/doi.org\/10.1002\/chem.201703539","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2017,11,16]]}}}