Theoretical study of the energetics of carboxylic O–H bond cleavage in the para- and meta-substituted benzoic acid derivatives

Peter Škorňa; Adam Vagánek; Peter Poliak; Erik Klein

doi:10.1515/acs-2015-0013

Abstract

Gas phase bond dissociation enthalpies (BDE) of para- and meta-substituted benzoic acids and proton affinities (PA) of their carboxylate anions were investigated using the B3LYP/6-311++G** method for 15 substituents with various electron-donating and electron-withdrawing effects. The employed computational method provided BDE and PA values in fair agreement with experimental data. The substituent effect on BDEs and PAs was analyzed in terms of Hammett constants. Found dependences exhibit satisfactory linearity and enable quick estimation of BDEs and PAs from the Hammett constants.

References

Álvarez-Diduk R, Ramírez-Silva MT, Galano A, Merkoçi A (2013) J. Phys. Chem. B 117: 12347–12359.
Search in Google Scholar
Bakalbassis EG, Lithoxoidou AT, Vafiadis AP (2003) J. Phys. Chem. A 107: 8594–8606.
Search in Google Scholar
Becke AD (1988) Phys. Rev. A 38: 3098–3100.
Search in Google Scholar
Bordwell FG, Zhang X-M, Satish AV, Cheng J-P (1994) J. Am. Chem. Soc. 116: 6605–6610.
Search in Google Scholar
Curtiss LA, McGrath MP, Blandeau J-P, Davis NE, Binning RC Jr, Radom L (1995) J. Chem. Phys. 103: 6104–6113.
Search in Google Scholar
Denisov ET, Tumanov VE (2005) Pet. Chem. 45: 237–248.
Search in Google Scholar
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 Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford CT.
Search in Google Scholar
Galaverna RS, Bataglion GA, Heerdt G, De Sa GF, Daroda R, Cunha VS, Morgon NH, Eberlin MN (2015) Eur. J. Org. Chem. 2015, 2189–2196.
Search in Google Scholar
Halliwell B, Gutteridge JMC (1989) Free Radicals in Biology and Medicine, 2nd ed., Clarendon: Oxford.
Search in Google Scholar
Hansch C, Leo A, Taft RW (1991) Chem. Rev. 91: 165–195.
Search in Google Scholar
Klein E, Lukeš V (2006a) J. Phys. Chem. A 110: 12312–12320.10.1021/jp063468i17078630
Search in Google Scholar
Klein E, Lukeš V (2006b) J. Mol. Struct.: THEOCHEM 767: 43–50.10.1016/j.theochem.2006.04.017
Search in Google Scholar
Krishnan R, Binkley JS, Seeger R, Pople JA (1980) J. Chem. Phys. 72: 650–654.
Search in Google Scholar
Krygowski TM, Stępień BT (2005) Chem. Rev. 105: 3482–3512.
Search in Google Scholar
Lee C, Yang W, Parr RG (1988) Phys. Rev. B 37: 785–789.
Search in Google Scholar
Lemańska K, Szymusiak H, Tyrakowska B, Zieliński R, Soffers AEMF, Rietjens IMCM (2001) Free Rad. Biol. Med. 31: 869–881.
Search in Google Scholar
Luo Y-R (2007) Comprehensive handbook of chemical bond energies. CRC Press: Boca Raton.10.1201/9781420007282
Search in Google Scholar
McLean AD, Chandler GS (1980) J. Chem. Phys. 72: 5639–5648.
Search in Google Scholar
McMahon TB, Kebarle P (1977) J. Am. Chem. Soc. 99: 2222–2230.
Search in Google Scholar
Musialik M, Kuzmicz R, Pawlowski TS, Litwinienko G (2009) J. Org. Chem. 74: 2699–2709.
Search in Google Scholar
Rimarčík J, Lukeš V, Klein E, Rottmannová L (2011) Comp. Theor. Chem. 967: 273–283.
Search in Google Scholar
Vagánek A, Rimarčík J, Dropková K, Lengyel J, Klein E (2014) Comp. Theor. Chem. 1050: 31–38.
Search in Google Scholar

Theoretical study of the energetics of carboxylic O–H bond cleavage in the para- and meta-substituted benzoic acid derivatives

Abstract

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