{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,26]],"date-time":"2026-02-26T15:18:39Z","timestamp":1772119119625,"version":"3.50.1"},"reference-count":32,"publisher":"Springer Science and Business Media LLC","issue":"9","license":[{"start":{"date-parts":[[2023,8,18]],"date-time":"2023-08-18T00:00:00Z","timestamp":1692316800000},"content-version":"tdm","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0"},{"start":{"date-parts":[[2023,8,18]],"date-time":"2023-08-18T00:00:00Z","timestamp":1692316800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0"}],"funder":[{"name":"Iacobus Program"},{"DOI":"10.13039\/501100010801","name":"Xunta de Galicia","doi-asserted-by":"crossref","award":["GRC 2019\/24"],"award-info":[{"award-number":["GRC 2019\/24"]}],"id":[{"id":"10.13039\/501100010801","id-type":"DOI","asserted-by":"crossref"}]},{"DOI":"10.13039\/501100010801","name":"Xunta de Galicia","doi-asserted-by":"crossref","award":["GRC 2019\/24"],"award-info":[{"award-number":["GRC 2019\/24"]}],"id":[{"id":"10.13039\/501100010801","id-type":"DOI","asserted-by":"crossref"}]},{"DOI":"10.13039\/501100006761","name":"Universidade de Vigo","doi-asserted-by":"crossref","id":[{"id":"10.13039\/501100006761","id-type":"DOI","asserted-by":"crossref"}]}],"content-domain":{"domain":["link.springer.com"],"crossmark-restriction":false},"short-container-title":["Theor Chem Acc"],"published-print":{"date-parts":[[2023,9]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    24 substituted cyanocompounds and the corresponding anions obtained upon H\n                    <jats:sup>+<\/jats:sup>\n                    -abstraction from diverse positions were subjected to an electron density analysis with the quantum theory of atoms in molecules (QTAIM). All the electron densities were obtained at the B3LYP\/6\u201331\u2009+\u2009\u2009+\u2009G(2d,2p) level on completely optimized geometries. In accordance to experimental evidence, \u03b1-H\n                    <jats:sup>+<\/jats:sup>\n                    abstraction is found as the most favored one (by at least 100\u00a0kJ\u00a0mol\n                    <jats:sup>\u22121<\/jats:sup>\n                    in all the tested compounds). The presence of additional resonance electron attractors reduces significantly the \u03b1-deprotonation energy, whereas this magnitude is quite insensitive to the inclusion of resonance electron donors. The electron density rearrangement accompanying the deprotonation is apparently in line with the predictions of the resonance model (RM). In fact, a significant part of the electron density gained by expelling the proton is transferred to cyano N and to other groups where significant resonance structures delocalize the negative charge. Nevertheless, some significant modifications have to be introduced on the RM picture when the QTAIM results are studied in detail.\n                  <\/jats:p>","DOI":"10.1007\/s00214-023-03022-8","type":"journal-article","created":{"date-parts":[[2023,8,18]],"date-time":"2023-08-18T08:02:15Z","timestamp":1692345735000},"update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Electron density analysis on the alpha acidity of nitriles"],"prefix":"10.1007","volume":"142","author":[{"given":"Jos\u00e9 Luis","family":"L\u00f3pez","sequence":"first","affiliation":[]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8786-0086","authenticated-orcid":false,"given":"Filipe","family":"Teixeira","sequence":"additional","affiliation":[]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0794-2215","authenticated-orcid":false,"given":"Ana M.","family":"Gra\u00f1a","sequence":"additional","affiliation":[]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8252-9212","authenticated-orcid":false,"given":"Ricardo A.","family":"Mosquera","sequence":"additional","affiliation":[]}],"member":"297","published-online":{"date-parts":[[2023,8,18]]},"reference":[{"key":"3022_CR1","volume-title":"Comprehensive organic synthesis","author":"P Knochel","year":"2014","unstructured":"Knochel P, Molander GA (2014) Comprehensive organic synthesis. Elsevier, Amsterdam"},{"key":"3022_CR2","doi-asserted-by":"crossref","unstructured":"Richard JP (1990) In: Rappoport Z (ed) The Chemistry of Enols. Wiley, New York","DOI":"10.1002\/9780470772294.ch11"},{"key":"3022_CR3","volume-title":"Advanced organic chemistry","author":"FA Carey","year":"2001","unstructured":"Carey FA, Sundberg RJ (2001) Advanced organic chemistry. Kluwer Academic, New York"},{"key":"3022_CR4","volume-title":"Resonance in organic chemistry","author":"GW Wheland","year":"1955","unstructured":"Wheland GW (1955) Resonance in organic chemistry. Wiley, New York"},{"key":"3022_CR5","doi-asserted-by":"publisher","first-page":"7424","DOI":"10.1039\/c5cp03805g","volume":"17","author":"D Ferro-Costas","year":"2015","unstructured":"Ferro-Costas D, Mosquera RA (2015) Excluding hyperconjugation from the Z conformational preference and investigating its origin: formic acid and beyond. Phys Chem Chem Phys 17:7424\u20137434. https:\/\/doi.org\/10.1039\/c5cp03805g","journal-title":"Phys Chem Chem Phys"},{"key":"3022_CR6","doi-asserted-by":"publisher","first-page":"5935","DOI":"10.1021\/ja00254a006","volume":"109","author":"KB Wiberg","year":"1987","unstructured":"Wiberg KB, Laidig KE (1987) Barriers to rotation adjacent to double bonds. 3. The carbon-oxygen barrier in formic acid, methyl formate, acetic acid, and methyl acetate. The origin of ester and amide resonance. J Am Chem Soc 109:5935\u20135943. https:\/\/doi.org\/10.1021\/ja00254a006","journal-title":"J Am Chem Soc"},{"key":"3022_CR7","doi-asserted-by":"publisher","first-page":"831","DOI":"10.1021\/ja00029a005","volume":"114","author":"KB Wiberg","year":"1992","unstructured":"Wiberg KB, Breneman CM (1992) Resonance interactions in acyclic systems. 3. Formamide internal rotation revisited. Charge and energy redistribution along the C\u2013N bond rotational pathway. J Am Chem Soc 114:831\u2013840. https:\/\/doi.org\/10.1021\/ja00029a005","journal-title":"J Am Chem Soc"},{"key":"3022_CR8","doi-asserted-by":"publisher","first-page":"2961","DOI":"10.1139\/v88-459","volume":"66","author":"TS Slee","year":"1988","unstructured":"Slee TS, MacDougall PJ (1988) The correspondence between H\u00fcckel theory and ab initio atomic charges in allyl ions. Can J Chem 66:2961\u20132962. https:\/\/doi.org\/10.1139\/v88-459","journal-title":"Can J Chem"},{"key":"3022_CR9","doi-asserted-by":"publisher","first-page":"7912","DOI":"10.1021\/ja00046a047","volume":"114","author":"KE Laidig","year":"1992","unstructured":"Laidig KE (1992) Use of nuclear potential to investigate the atomic size dependency of populations defined within the theory of atoms in molecules. J Am Chem Soc 114:7912\u20137913. https:\/\/doi.org\/10.1021\/ja00046a047","journal-title":"J Am Chem Soc"},{"key":"3022_CR10","doi-asserted-by":"publisher","first-page":"1737","DOI":"10.1021\/ja952678y","volume":"118","author":"KE Laidig","year":"1996","unstructured":"Laidig KE, Cameron LM (1996) Barrier to rotation in thioformamide: implications for amide Resonance. J Am Chem Soc 118:1737\u20131742. https:\/\/doi.org\/10.1021\/ja952678y","journal-title":"J Am Chem Soc"},{"key":"3022_CR11","doi-asserted-by":"publisher","first-page":"7993","DOI":"10.1021\/j100361a009","volume":"93","author":"R Glaser","year":"1989","unstructured":"Glaser R (1989) Diazonium ions: a theoretical study of pathways to automerization, thermodynamic stabilities, and topological electron density analysis of the bonding. J Phys Chem 93:7993\u20138003. https:\/\/doi.org\/10.1021\/j100361a009","journal-title":"J Phys Chem"},{"key":"3022_CR12","doi-asserted-by":"publisher","unstructured":"Glaser R, Choy GSC. Importance of the anisotropy of atoms in molecules for the representation of electron density distributions with Lewis structures. A case study of aliphatic diazonium ions. J Am Chem Soc. 115:2340\u20132347 https:\/\/doi.org\/10.1021\/ja00059a031.","DOI":"10.1021\/ja00059a031"},{"key":"3022_CR13","doi-asserted-by":"publisher","first-page":"9257","DOI":"10.1021\/ja00099a049","volume":"116","author":"P Speers","year":"1994","unstructured":"Speers P, Laidig KE, Streitwieser A (1994) Origins of the acidity trends in dimethyl sulfide, dimethyl sulfoxide, and dimethyl sulfone. J Am Chem Soc 116:9257\u20139261. https:\/\/doi.org\/10.1021\/ja00099a049","journal-title":"J Am Chem Soc"},{"key":"3022_CR14","doi-asserted-by":"publisher","first-page":"9415","DOI":"10.1016\/S0040-4020(01)00946-2","volume":"57","author":"A Vila","year":"2001","unstructured":"Vila A, Mosquera RA (2001) Electron density analysis of small ring ethers. Tetrahedron 57:9415\u20139422. https:\/\/doi.org\/10.1016\/S0040-4020(01)00946-2","journal-title":"Tetrahedron"},{"key":"3022_CR15","doi-asserted-by":"publisher","first-page":"5361","DOI":"10.1021\/jp034451s","volume":"107","author":"MJ Gonz\u00e1lez Moa","year":"2003","unstructured":"Gonz\u00e1lez Moa MJ, Mosquera RA (2003) Applicability of resonance forms in pyrimidinic bases. An AIM study. J Phys Chem A 107:5361\u20135367. https:\/\/doi.org\/10.1021\/jp034451s","journal-title":"J Phys Chem A"},{"key":"3022_CR16","doi-asserted-by":"publisher","first-page":"3682","DOI":"10.1021\/jp044529k","volume":"109","author":"MJ Gonz\u00e1lez Moa","year":"2005","unstructured":"Gonz\u00e1lez Moa MJ, Mosquera RA (2005) On the applicability of resonance forms in pyrimidinic bases. II. QTAIM interpretation of the sequence of protonation affinities. J Phys Chem A 109:3682\u20133686. https:\/\/doi.org\/10.1021\/jp044529k","journal-title":"J Phys Chem A"},{"key":"3022_CR17","doi-asserted-by":"publisher","first-page":"255","DOI":"10.1016\/j.cplett.2006.07.073","volume":"428","author":"MJ Gonz\u00e1lez Moa","year":"2006","unstructured":"Gonz\u00e1lez Moa MJ, Mandado M, Mosquera RA (2006) Explaining the sequence of protonation affinities of cytosine with QTAIM. Chem Phys Lett 428:255\u2013261. https:\/\/doi.org\/10.1016\/j.cplett.2006.07.073","journal-title":"Chem Phys Lett"},{"key":"3022_CR18","doi-asserted-by":"publisher","first-page":"2652","DOI":"10.1021\/jp811023x","volume":"113","author":"JL L\u00f3pez","year":"2009","unstructured":"L\u00f3pez JL, Gra\u00f1a AM, Mosquera RA (2009) Electron density analysis on the protonation of nitriles. J Phys Chem A 113:2652\u20132657. https:\/\/doi.org\/10.1021\/jp811023x","journal-title":"J Phys Chem A"},{"key":"3022_CR19","doi-asserted-by":"publisher","first-page":"7050","DOI":"10.1021\/jp049338w","volume":"108","author":"M Mandado","year":"2004","unstructured":"Mandado M, Van Alsenoy C, Mosquera RA (2004) Comparison of the AIM and Hirshfeld totals, \u03c3, and \u03c0 charge distributions: a study of protonation and hydride addition processes. J Phys Chem A 108:7050\u20137055. https:\/\/doi.org\/10.1021\/jp049338w","journal-title":"J Phys Chem A"},{"key":"3022_CR20","doi-asserted-by":"publisher","first-page":"106","DOI":"10.1016\/j.cplett.2005.06.096","volume":"412","author":"AM Gra\u00f1a","year":"2005","unstructured":"Gra\u00f1a AM, Hermida-Ram\u00f3n JM, Mosquera RA (2005) QTAIM interpretation of the basicity of substituted anilines. Chem Phys Lett 412:106\u2013109. https:\/\/doi.org\/10.1016\/j.cplett.2005.06.096","journal-title":"Chem Phys Lett"},{"key":"3022_CR21","doi-asserted-by":"publisher","first-page":"454","DOI":"10.1016\/j.cplett.2004.01.084","volume":"386","author":"M Mandado","year":"2004","unstructured":"Mandado M, Mosquera RA, Gra\u00f1a AM (2004) AIM interpretation of the acidity of phenol derivatives. Chem Phys Lett 386:454\u2013459. https:\/\/doi.org\/10.1016\/j.cplett.2004.01.084","journal-title":"Chem Phys Lett"},{"key":"3022_CR22","doi-asserted-by":"publisher","first-page":"10","DOI":"10.1016\/j.cplett.2005.02.011","volume":"405","author":"M Mandado","year":"2005","unstructured":"Mandado M, Van Alsenoy C, Mosquera RA (2005) Electron charge redistribution upon hydride addition to carbonylic compounds. Chem Phys Lett 405:10\u201317. https:\/\/doi.org\/10.1016\/j.cplett.2005.02.011","journal-title":"Chem Phys Lett"},{"key":"3022_CR23","doi-asserted-by":"publisher","first-page":"8624","DOI":"10.1021\/jp051953s","volume":"109","author":"M Mandado","year":"2005","unstructured":"Mandado M, Van Alsenoy C, Mosquera RA (2005) Joint QTAIM and hirshfeld study of the \u03c3 and \u03c0 charge distribution and electron delocalization in carbonyl compounds: a comparative study with the resonance model. J Phys Chem A 109:8624\u20138631. https:\/\/doi.org\/10.1021\/jp051953s","journal-title":"J Phys Chem A"},{"key":"3022_CR24","doi-asserted-by":"publisher","first-page":"249","DOI":"10.1016\/j.cplett.2006.07.059","volume":"428","author":"N Otero","year":"2006","unstructured":"Otero N, Gonz\u00e1lez Moa MJ, Mandado M, Mosquera RA (2006) QTAIM study of the protonation of indole. Chem Phys Lett 428:249\u2013254. https:\/\/doi.org\/10.1016\/j.cplett.2006.07.059","journal-title":"Chem Phys Lett"},{"key":"3022_CR25","doi-asserted-by":"publisher","first-page":"2403","DOI":"10.1002\/ejoc.201101407","volume":"12","author":"N Otero","year":"2012","unstructured":"Otero N, Est\u00e9vez L, Mandado M, Mosquera RA (2012) An electron-density-based study on the ionic reactivity of 1,3-azoles. Eur J Org Chem 12:2403\u20132413. https:\/\/doi.org\/10.1002\/ejoc.201101407","journal-title":"Eur J Org Chem"},{"key":"3022_CR26","doi-asserted-by":"publisher","unstructured":"Est\u00e9vez L, Mosquera RA (2008) Where is the positive charge of flavylium cations? Chem. Phys. Lett. 451:121\u2013126. https:\/\/doi.org\/10.1016\/j.cplett.2007.11.065","DOI":"10.1016\/j.cplett.2007.11.065"},{"key":"3022_CR27","doi-asserted-by":"crossref","DOI":"10.1093\/oso\/9780198551683.001.0001","volume-title":"Atoms in Molecules: A Quantum Theory","author":"RFW Bader","year":"1990","unstructured":"Bader RFW (1990) Atoms in Molecules: A Quantum Theory. Oxford University Press, New York"},{"key":"3022_CR28","doi-asserted-by":"publisher","first-page":"893","DOI":"10.1021\/cr00005a013","volume":"91","author":"RFW Bader","year":"1991","unstructured":"Bader RFW (1991) A quantum theory of molecular structure and its applications. Chem Rev 91:893. https:\/\/doi.org\/10.1021\/cr00005a013","journal-title":"Chem Rev"},{"key":"3022_CR29","doi-asserted-by":"publisher","first-page":"379","DOI":"10.1016\/j.cplett.2005.03.078","volume":"407","author":"DR Alcoba","year":"2005","unstructured":"Alcoba DR, Lain L, Torre A, Bochicchio RC (2005) Treatments of non-nuclear attractors within the theory of atoms in molecules. Chem Phys Lett 407:379\u2013383. https:\/\/doi.org\/10.1016\/j.cplett.2005.03.078","journal-title":"Chem Phys Lett"},{"key":"3022_CR30","unstructured":"Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas \u00d6, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2016) Gaussian09 revision D.01. Gaussian Inc, Wallingford CT."},{"key":"3022_CR31","unstructured":"Bader RFW. AIMPAC: a suite of programs for the AIM theory. Mc Master University, Hamilton, Ontario, Canada."},{"key":"3022_CR32","doi-asserted-by":"publisher","first-page":"7135","DOI":"10.1021\/ja00019a008","volume":"113","author":"Y Aray","year":"1991","unstructured":"Aray Y, Murgich J, Luna MA (1991) Substituent effects and the charge topology in nitriles and cyanides. J Am Chem Soc 113:7135\u20137143. https:\/\/doi.org\/10.1021\/ja00019a008","journal-title":"J Am Chem Soc"}],"container-title":["Theoretical Chemistry Accounts"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/link.springer.com\/content\/pdf\/10.1007\/s00214-023-03022-8.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/link.springer.com\/article\/10.1007\/s00214-023-03022-8\/fulltext.html","content-type":"text\/html","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/link.springer.com\/content\/pdf\/10.1007\/s00214-023-03022-8.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,12,19]],"date-time":"2023-12-19T02:53:53Z","timestamp":1702954433000},"score":1,"resource":{"primary":{"URL":"https:\/\/link.springer.com\/10.1007\/s00214-023-03022-8"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,8,18]]},"references-count":32,"journal-issue":{"issue":"9","published-print":{"date-parts":[[2023,9]]}},"alternative-id":["3022"],"URL":"https:\/\/doi.org\/10.1007\/s00214-023-03022-8","relation":{"has-preprint":[{"id-type":"doi","id":"10.21203\/rs.3.rs-2876440\/v1","asserted-by":"object"}]},"ISSN":["1432-881X","1432-2234"],"issn-type":[{"value":"1432-881X","type":"print"},{"value":"1432-2234","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,8,18]]},"assertion":[{"value":"29 April 2023","order":1,"name":"received","label":"Received","group":{"name":"ArticleHistory","label":"Article History"}},{"value":"13 July 2023","order":2,"name":"accepted","label":"Accepted","group":{"name":"ArticleHistory","label":"Article History"}},{"value":"18 August 2023","order":3,"name":"first_online","label":"First Online","group":{"name":"ArticleHistory","label":"Article History"}},{"order":1,"name":"Ethics","group":{"name":"EthicsHeading","label":"Declarations"}},{"value":"The authors declare that there are no conflicts of interest.","order":2,"name":"Ethics","group":{"name":"EthicsHeading","label":"Conflict of interest"}},{"value":"Not applicable.","order":3,"name":"Ethics","group":{"name":"EthicsHeading","label":"Consent to participate and for publication"}}],"article-number":"87"}}