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The α-C–H BDE in tetralin

A time-resolved photoacoustic calorimetry study

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Abstract

The α-C–H bond dissociation enthalpy (BDE) in tetralin (1,2,3,4-tetrahydronaphtalene) was determined using time-resolved photoacoustic calorimetry as 357.6 ± 5.4 kJ mol−1. This value is some 10 kJ mol−1 higher than the only previous experimental determination but in remarkably good agreement with the α-C–H BDEs in the structurally related compounds such as 1-butene, cyclohexene, and ethylbenzene.

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Notes

  1. The result is the average of seven independent experiments, and the uncertainty is twice the standard deviation of the mean (sdm), according to the thermochemical convention. It is important to note that most authors identify the uncertainty in BDEs with the sdm.

References

  1. Arends IWCE, Mulder P, Clark KB, Wayner DDM. Rate constants for termination and TEMPO trapping of some resonance stabilized hydroaromatic radicals in the liquid phase. J Phys Chem. 1995;99:8182–9.

    Article  CAS  Google Scholar 

  2. Laarhoven LJJ, Mulder P. α-C–H bond strengths in tetralin and THF: application of competition experiments in photoacoustic calorimetry. J Phys Chem B. 1997;101:73–7.

    Article  CAS  Google Scholar 

  3. Finn M, Friedline R, Suleman NK, Wohl CJ, Tanko JM. Chemistry of the t-butoxyl radical: evidence that most hydrogen abstractions from carbon are entropy-controlled. J Am Chem Soc. 2004;126:7578–84.

    Article  CAS  Google Scholar 

  4. Muralha VS, Borges dos Santos RM, Martinho Simões JA. Energetics of alkylbenzyl radicals: a time-resolved photoacoustic calorimetry study. J Phys Chem A. 2004;108:936–42.

    Article  CAS  Google Scholar 

  5. Agapito F, Nunes PM, Costa Cabral BJ, Borges dos Santos RM, Martinho Simões JA. Energetics of the Allyl Group. J Org Chem. 2007;72:8770–9.

    Article  CAS  Google Scholar 

  6. Agapito F, Nunes PM, Costa Cabral BJ, Borges dos Santos RM, Martinho Simões JA. Energetic differences between the five- and six-membered ring hydrocarbons: strain energies in the parent and radical molecules. J Org Chem. 2008;73:6213–23.

    Article  CAS  Google Scholar 

  7. Diogo HP, Minas da Piedade ME, Martinho Simões JA, Nagano Y. Standard enthalpy of formation and enthalpy of vaporization of di-1, 1-dimethylethyl peroxide—reevaluation of the standard enthalpy of formation of the di-1, 1-dimethylethoxy radical. J Chem Thermodyn. 1995;27:597–604.

    Article  CAS  Google Scholar 

  8. Braslavsky SE, Heibel GE. Time-resolved photothermal and photoacoustic methods applied to photoinduced processes in solution. Chem Rev. 1992;92:1381–410.

    Article  CAS  Google Scholar 

  9. Peters KS. Time-resolved photoacoustic calorimetry: from carbenes to proteins. Angew Chem Int Ed Engl. 1994;33:294–302.

    Article  Google Scholar 

  10. Nunes PM, Agapito F, Costa Cabral BJ, Borges dos Santos RM, Martinho Simões JA. Enthalpy of formation of the cyclopentadienyl radical: photoacoustic calorimetry and ab initio studies. J Phys Chem A. 2006;110:5130–4.

    Article  CAS  Google Scholar 

  11. Borges dos Santos RM, Lagoa ALC, Martinho Simões JA. Photoacoustic calorimetry. An examination of a non-classical thermochemistry tool. J Chem Thermodyn. 1999;31:1483–510.

    Article  CAS  Google Scholar 

  12. Correia CF, Nunes PM, Borges dos Santos RM, Martinho Simões JA. Gas-phase energetics of organic free radicals using time-resolved photoacoustic calorimetry. Thermochim Acta. 2004;420:3–11.

    Article  CAS  Google Scholar 

  13. Rudzki JE, Goodman JL, Peters KS. Simultaneous determination of photoreaction dynamics and energetics using pulsed, time-resolved photoacoustic calorimetry. J Am Chem Soc. 1985;107:7849–54.

    Article  CAS  Google Scholar 

  14. Sound Analysis. Version 1.50D. Spokane, WA: Quantum Northwest; 1999.

  15. Nunes PM, Correia CF, Borges dos Santos RM, Martinho Simões JA. Time-resolved photoacoustic calorimetry as a tool to determine rate constants of hydrogen-abstraction reactions. Int J Chem Kinet. 2006;38:357–63.

    Article  CAS  Google Scholar 

  16. Wayner DDM, Lusztyk E, Pagé D, Ingold KU, Mulder P, Laarhoven LJJ, et al. Effects of solvation on the enthalpies of reaction of tert-butoxyl radicals with phenol and on the calculated O–H bond strength in phenol. J Am Chem Soc. 1995;117:8737–44.

    Article  CAS  Google Scholar 

  17. Borges dos Santos RM, Costa Cabral BJ, Martinho Simões JA. Bond dissociation enthalpies in the gas phase and in organic solvents: making ends meet. Pure Appl Chem. 2007;79:1369–82.

    Article  CAS  Google Scholar 

  18. Luo YR. Comprehensive handbook of chemical bond energies. Boca Raton: CRC Press; 2007.

    Book  Google Scholar 

  19. Agapito F, Nunes PM, Costa Cabral BJ, Borges dos Santos RM, Martinho Simões JA, to be published.

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Acknowledgements

This work was supported by Fundação para a Ciência e a Tecnologia (FCT), Portugal (PTDC/QUI/65535/2006). P. M. N. thanks FCT for a post-doctoral (SFRH/BPD/26677/2006) grant.

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Authors and Affiliations

  1. Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016, Lisbon, Portugal

    Rui M. Borges dos Santos, Paulo M. Nunes & José A. Martinho Simões

  2. Instituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa, Av. da República, 2780-157, Oeiras, Portugal

    Rui M. Borges dos Santos & José A. Martinho Simões

  3. Institute for Biotechnology and Bioengineering, Centro de Biomedicina Molecular e Estrutural, Universidade do Algarve, Campus de Gambelas, 8005-139, Faro, Portugal

    Rui M. Borges dos Santos

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  1. Rui M. Borges dos Santos
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  2. Paulo M. Nunes
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  3. José A. Martinho Simões
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Correspondence to Rui M. Borges dos Santos.

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Borges dos Santos, R.M., Nunes, P.M. & Martinho Simões, J.A. The α-C–H BDE in tetralin. J Therm Anal Calorim 100, 381–384 (2010). https://doi.org/10.1007/s10973-009-0632-0

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  • DOI: https://doi.org/10.1007/s10973-009-0632-0

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