Abstract
Bond dissociation enthalpies (BDEs) are computed using the Density Functional Theory (DFT) for a selected set of C–Br, C–O, and C–Br bonds susceptible to homolysis in the thermal degradation of four brominated flame retardants (BFRs): decabromo-diphenyl, decabromo-diphenylethane, 1,2-bis(2,4,6-tribromophenoxy)-ethane, and 3,4,5,6-tetrabromo-1,2-diethyl-phtalate. Based on BDEs computed at M06/cc-pVTZ level, choice based on a previous benchmark, we find debromination as the dominant decomposition pathway of brominated diphenyls and brominated phtalates, whereas scission to form brominated phenoxyls and benzyl radicals is preferred in aromatic BFRs containing ether and alkyl bridges, respectively. Trends in computed BDEs are rationalized in terms of (de)localization of spin density in the electronic structure of the resulting radicals.
Similar content being viewed by others
References
Rudel RA, Perovich LJ (2009) Endocrine disrupting chemicals in indoor and outdoor air. Atmos Environ 43:170–181. https://doi.org/10.1016/j.atmosenv.2008.09.025
Harrad S, de Wit CA, Abdallah MA-E et al (2010) Indoor contamination with Hexabromocyclododecanes, Polybrominated diphenyl ethers, and Perfluoroalkyl compounds: an important exposure pathway for people? Environ Sci Technol 44:3221–3231. https://doi.org/10.1021/es903476t
Covaci A, Harrad S, Abdallah MA-E et al (2011) Novel brominated flame retardants: a review of their analysis, environmental fate and behaviour. Environ Int 37:532–556. https://doi.org/10.1016/j.envint.2010.11.007
Van den Eede N, Dirtu AC, Ali N et al (2012) Multi-residue method for the determination of brominated and organophosphate flame retardants in indoor dust. Talanta 89:292–300. https://doi.org/10.1016/j.talanta.2011.12.031
Dirtu AC, Covaci A, Dirtu AC, Abdallah M (2013) Advances in the sample preparation of brominated flame retardants and other brominated compounds. TrAC Trends Anal Chem 43:189–203. https://doi.org/10.1016/j.trac.2012.10.004
Dirtu AC, Ravindra K, Roosens L et al (2008) Fast analysis of decabrominated diphenyl ether using low-pressure gas chromatography–electron-capture negative ionization mass spectrometry. J Chromatogr A 1186:295–301. https://doi.org/10.1016/j.chroma.2007.07.034
Luo J, Hu J, Wei X et al (2015) Dehalogenation of persistent halogenated organic compounds: a review of computational studies and quantitative structure-property relationships. Chemosphere 131:17–33. https://doi.org/10.1016/j.chemosphere.2015.02.013
Wilkie CA, Morgan AB (2009) Fire retardancy of polymeric materials, 2nd edn. CRC Press: Taylor & Francis Group, Boca Raton, p 527
Shih YH, Wang CK (2009) Photolytic degradation of polybromodiphenyl ethers under UV-lamp and solar irradiations. J Hazard Mater 165:34–38. https://doi.org/10.1016/j.jhazmat.2008.09.103
Pan L, Bian W (2013) Theoretical study on the photodegradation mechanism of nona-BDEs in methanol. ChemPhysChem 14:1264–1271. https://doi.org/10.1002/cphc.201200952
Rotko G, Romańczyk PP, Kurek SS (2013) Reductive debromination of decabromodiphenyl ether yields brominated dibenzofurans in a Pschorr-type cyclisation. Electrochem Commun 37:64–67. https://doi.org/10.1016/j.elecom.2013.10.010
Yu K, Gu C, Boyd SA et al (2012) Rapid and extensive Debromination of Decabromodiphenyl ether by Smectite clay-templated subnanoscale zero-valent iron. Environ Sci Technol 46:8969–8975. https://doi.org/10.1021/es300516e
Zhuang Y, Ahn S, Seyfferth AL et al (2011) Dehalogenation of Polybrominated diphenyl ethers and polychlorinated biphenyl by bimetallic, impregnated, and nanoscale Zerovalent iron. Environ Sci Technol 45:4896–4903. https://doi.org/10.1021/es104312h
Balabanovich A, Luda M, Camino G, Hornung A (2003) Thermal decomposition behavior of 1,2-bis-(2,4,6-tribromophenoxy)ethane. J Anal Appl Pyrolysis 67:95–107. https://doi.org/10.1016/S0165-2370(02)00020-7
Striebich RC, Rubey WA, Tirey DA, Dellinger B (1991) High-temperature degradation of polybrominated flame retardant materials. Chemosphere 23:1197–1204. https://doi.org/10.1016/0045-6535(91)90144-3
Altarawneh M, Dlugogorski BZ (2014) Thermal decomposition of 1,2-Bis(2,4,6-tribromophenoxy)ethane (BTBPE), a novel brominated flame retardant. Environ Sci Technol 48:14335–14343. https://doi.org/10.1021/es5038047
Maftei D, Dumitras M, Isac D-L, Dirtu AC (2016) Density functional study of bond dissociation energies in highly brominated diphenyl ethers. Studia Universitatis Babes-Bolyai. Chemia 61:137–146
Gaussian 09, Revision C.01, Frisch MJ, Trucks G W, Schlegel HB, Scuseria GE, Robb MA, Cheeseman J R, 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, Gaussian, Inc., Wallingford, 2009
Zhao Y, Truhlar DG (2008) The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other function. Theor Chem Accounts 120:215–241. https://doi.org/10.1007/s00214-007-0310-x
Li X, Xu X, You X, Truhlar DG (2016) Benchmark calculations for bond dissociation enthalpies of unsaturated methyl esters and the bond dissociation enthalpies of methyl Linolenate. J Phys Chem A. https://doi.org/10.1021/acs.jpca.6b02600
Ahubelem N, Altarawneh M, Dlugogorski BZ (2014) Dehydrohalogenation of ethyl halides. Tetrahedron Lett 55:4860–4868. https://doi.org/10.1016/j.tetlet.2014.07.009
Altarawneh M, Dlugogorski BZ (2015) Formation of dibenzofuran, dibenzo-p-dioxin and their hydroxylated derivatives from catechol. Phys Chem Chem Phys 17:1822–1830. https://doi.org/10.1039/C4CP04168B
Köppen R, Emmerling F, Becker R (2007) Decabromodiphenylethane. Acta Crystallogr Sect E Struct Rep Online 63:o585–o586. https://doi.org/10.1107/S1600536807000219
Yasuoka N, Ando T, Kuriyabashi S (1967) The crystal structure of 1,2-Diphenoxyethane. Bull Chem Soc Jpn 40:270–273. https://doi.org/10.1246/bcsj.40.270
Dunning TH (2000) A road map for the calculation of molecular binding energies. J Phys Chem A 104:9062–9080. https://doi.org/10.1021/jp001507z
McMillen DF, Golden DM (1982) Hydrocarbon bond dissociation energies. Annu Rev Phys Chem 33:493–532. https://doi.org/10.1146/annurev.pc.33.100182.002425
Kominar RJ, Krech MJ, Price SJW (1978) Pyrolysis of bromobenzene by the toluene carrier technique and determination of D (C 6 H 5 —Br). Can J Chem 56:1589–1592. https://doi.org/10.1139/v78-259
Blanksby SJ, Ellison GB (2003) Bond dissociation energies of organic molecules. Acc Chem Res 36:255–263. https://doi.org/10.1021/ar020230d
Altarawneh M, Dlugogorski BZ (2013) A mechanistic and kinetic study on the formation of PBDD/fs from PBDEs. Environ Sci Technol 47:5118–5127. https://doi.org/10.1021/es305081j
Acknowledgements
This research has been financed by a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS-UEFISCDI, project number PN-II-RU-TE-2014-4-1010.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Electronic supplementary material
ESM 1
(DOCX 25 kb)
Rights and permissions
About this article
Cite this article
Maftei, D., Isac, DL., Dumitraș, M. et al. Trends in bond dissociation energies of brominated flame retardants from density functional theory. Struct Chem 29, 921–927 (2018). https://doi.org/10.1007/s11224-018-1078-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11224-018-1078-4