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The hydrogen transfer reaction between the substance of triplet state thioxanthone and alkane with sp3 hybridization hydrogen

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Abstract

The activation or functionalization of the saturated C-H is an extremely active field at present. We have explored the triplet state thioxanthone in reactivity of the hydrogen transfer reaction between donors and acceptors. In our works, two donors with quasi-inert sp3 C-H of skipped diene (3,6-nonadiene) and cyclic acetals (benzodioxole) reacted with type II photoinitiators (triplet state of thioxanthone series, TXs) as acceptors are investigated. The excited energies of TXs were obtained by time-dependent density functional theory (TD-DFT). TXs show obvious photosensibility based on their low reorganization energies (< 60 kcal mol−1). The isoentropy reactions had linear geometries of transition state (TS). The distortion/interaction model was used to probe the existence of interaction between acceptors and donors in saddle point. The distortion energy and activation barrier of benzodioxole are much higher than those of the corresponding 3,6-nonadiene. The lower bond dissociation energy noticeably affect the transition state. The reaction of triplet state of TXs with skipped dienes were found to have an anomalous low tunneling factors by using Wigner correction and early transition state by using the bond-energy–bond-order method. The triplet state of TXs photoinitiator can induced the hydrogen abstraction from saturated cyclic acetals and the skipped alkadienes. The hydrogen abstraction experiment are confirmed by UV and real-time FTIR.

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References

  1. 1.

    Davies HML (2016) Recent advances in catalytic enantioselective intermolecular C-H functionalization. Angew Chem Int Ed 45(39):6422–6425. https://doi.org/10.1002/anie.200601814

  2. 2.

    Davies HML, James RM (2008) Catalytic C–H functionalization by metal carbenoid and nitrenoid insertion. Nature 451(7177):417–424. https://doi.org/10.1038/nature06485

  3. 3.

    Jay AL, John EB (2002) Understanding and exploiting C–H bond activation. Nature 417(6888):507–514. https://doi.org/10.1038/417507a

  4. 4.

    Zhou H, Huang YG, Zhang Y, Song DD, Huang H, Zhong C, Ye GD (2016) Hydrogen abstraction of carbon/phosphorus-containing radicals in photoassisted polymerization. RSC Adv 6(73):68952–68959. https://doi.org/10.1039/C6RA00156D

  5. 5.

    Ye GD, Courtecuisse F, Allonas X, Ley C, Croutxe-Barghorn C, Raja P, Taylor P, Bescond G (2012) Photoassisted oxypolymerization of alkyd resins: kinetics and mechanisms. Prog Org Coat 73(4):366–373. https://doi.org/10.1016/j.porgcoat.2011.03.015

  6. 6.

    Zhou H, Song DD, Zhong C, Ye GD (2016) Theoretical and experimental study of light-assisted polymerization by multimechanism action. Sci Rep UK 6(1):38473. https://doi.org/10.1038/srep38473

  7. 7.

    Aydemir M, Baysal A, Özkar S, Yıldırım LT (2011) Ruthenium complexes of aminophosphine ligands and their use as pre-catalysts in the transfer hydrogenation of aromatic ketones: X-ray crystal structure of thiophene-2-(N-diphenylthiophosphino)methylamine. Polyhedron 30(5):796–804. https://doi.org/10.1016/j.poly.2010.12.011

  8. 8.

    Irmouli Y, George B, Merlin A (2009) Study of the polymerization of acrylic resins by photocalorimetry: interactions between UV initiators and absorbers. J Therm Anal Calorim 96(3):911–916. https://doi.org/10.1007/s10973-009-0061-0

  9. 9.

    Tehfe MA, Dumur F, Graff B, Morlet-Savary F, Fouassier JP, Gigmes D, Lalevée J (2012) Trifunctional photoinitiators based on a triazine skeleton for visible light source and UV LED induced polymerizations. Macromolecules 45(21):8639–8647. https://doi.org/10.1021/ma301931p

  10. 10.

    Warzeska ST, Zonneveld M, Van Gorkum R, Muizebelt WJ, Bouwman E, Reedijk J (2002) The influence of bipyridine on the drying of alkyd paints: a model study. Prog Org Coat 44(3):243–248. https://doi.org/10.1016/S0300-9440(02)00057-7

  11. 11.

    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA (2016) Gaussian 16. Gaussian Inc., Wallingford

  12. 12.

    Sébastien C, Frédéric B, Eric H (2013) KiSThelP: a program to predict thermodynamic properties and rate constants from quantum chemistry results. J Comput Chem 35(1):82–93. https://doi.org/10.1002/jcc.23470

  13. 13.

    Tian L, Feiwu C (2012) Multiwfn: a multifunctional wavefunction analyzer. J Comput Chem 33(5):580–592. https://doi.org/10.1002/jcc.22885

  14. 14.

    Stratmann RE, Scuseria GE, Frisch MJJ (1998) An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules. J Chem Phys 109(19):8281–8224. https://doi.org/10.1063/1.477483

  15. 15.

    Jacquemin D, Perpète EA, Ciofini I, Adamo C (2009) Accurate simulation of optical properties in dyes. Acc Chem Res 42(2):326–334. https://doi.org/10.1021/ar800163d

  16. 16.

    Peach MJG, Benfield P, Helgaker T, Tozer DJ (2008) Excitation energies in density functional theory: an evaluation and a diagnostic test. J Chem Phys 128(4):044118. https://doi.org/10.1063/1.2831900

  17. 17.

    Jacquemin D, Planchat A, Adamo C, Mennucci B (2012) TD-DFT assessment of Functionals for optical 0–0 transitions in solvated dyes. J Chem Theory Comput 8(7):2359–2372. https://doi.org/10.1021/ct300326f

  18. 18.

    Truhlar DG, Garrett BC, Klippenstein SJ (1996) Current status of Transition-State theory. J Phys Chem 100(31):12771–12800. https://doi.org/10.1021/jp953748q

  19. 19.

    Lee CT, Yang WT, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the Electron-density. Phys Rev B 37(2):785–789. https://doi.org/10.1103/PhysRevB.37.785

  20. 20.

    Jacquemin D, Perpète EA, Ciofini I, Adamo C (2010) Assessment of Functionals for TD-DFT calculations of singlet−triplet transitions. J Chem Theory Comput 6(5):1532–1537. https://doi.org/10.1021/ct100005d

  21. 21.

    Huang H, Liu HH, Zhou H, Liang ZL, Song DD, Zhang Y, Huang WQ, Zhao XT, Wu B, Ye GD, Huang YG (2019) Drug-release system of microchannel transport used in minimally invasive surgery for hemostasis. Drug Des Devel Ther 13:881–896. https://doi.org/10.2147/DDDT.S180842

  22. 22.

    Blowers P, Masel RI (1998) Conservation of bond order during radical substitution reactions: implications for the BEBO model. J Phys Chem A 102(48):9957–9964. https://doi.org/10.1021/jp9829243

  23. 23.

    Bickelhaupt FM, Houk KN (2017) Das distortion/interaction-activation-strain-Modell zur analyse von Reaktionsgeschwindigkeiten. Angew Chem 129(34):10204–10221. https://doi.org/10.1002/ange.201701486

  24. 24.

    Wolters LP, Bickelhaupt FM (2015) The activation strain model and molecular orbital theory. Wiley Interdiscip Rev Comput Mol Sci 5(4):324–343. https://doi.org/10.1002/wcms.1221

  25. 25.

    Liang ZL, Liu HH, Su NJ, Song DD, Zhang Y, Huang H, Zheng JQ, Zhong C, Ye GD (2018) Study of the deformation/interaction model: how interactions increase the reaction barrier. J Chem NY 2018:1–8. https://doi.org/10.1155/2018/3106297

  26. 26.

    Song DD, Wu B, Huang BY, Zhang Y, Huang H, Liang ZL, Ke ZF, Ye GD (2016) Comparative analysis of linear and non-linear transition state of hydrogen transfer reaction between benzoyl type radicals with skipped alkadienes. Comput Theor Chem 1081:25–29. https://doi.org/10.1016/j.comptc.2016.01.021

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Funding

The authors’ works are supported by the National Natural Science Foundation of China (Grant No. 21274032), the Natural Science Foundation of Guangdong Province (Grant No. 2014A030313500), and The Undergraduate Innovation and Entrepreneurship Training Program of Guangdong Province (Grant Numbers: 201810570083). This work was also funded by the Training Program for Academic Backbone in High-Level University (Grant Numbers: B185004195). The corresponding author, Guodong Ye, would like to thank the above funding sources. Xiaotian Zhao , Wanqiu Huang , Dandan Song are co-first authors

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Correspondence to Guodong Ye.

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Zhao, X., Huang, W., Song, D. et al. The hydrogen transfer reaction between the substance of triplet state thioxanthone and alkane with sp3 hybridization hydrogen. J Mol Model 26, 56 (2020). https://doi.org/10.1007/s00894-020-4300-4

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Keywords

  • Hydrogen transfer
  • Triplet state
  • Thioxanthone