Catalytic Mechanism of Interfacial Water in the Cycloaddition of Quadricyclane and Diethyl Azodicarboxylate

Embargo End Date
2022-03-18

Type
Article

Authors
Nguyen, Duy
Casillas, Sarah
Vang, Hnubci
Garcia, Anthony
Mizuno, Hikaru
Riffe, Erika J.
Saykally, Richard J.
Nguyen, Son C.

Online Publication Date
2021-03-18

Print Publication Date
2021-04-01

Date
2021-03-18

Abstract
“On-water” catalysis, the unusual activity of water molecules at the organic solvent–water interface, has been demonstrated in many organic reactions. However, the catalytic mechanism has remained unclear, largely because of the irreproducibility of the organic–water interface under the common stirring condition. Here, the interfacial area was controlled by employing adsorbed water on mesoporous silica nanoparticles as the catalyst. Reliable kinetics of the cycloaddition reaction of quadricyclane and diethyl azodicarboxylate (DEAD) at the toluene–water interface within the nanoparticle pores were measured. Data reveal an Eley–Rideal mechanism, wherein DEAD adsorbs at the toluene–water interface via hydrogen bonds formed with interfacial water, which lower the activation energy of the cycloaddition reaction. The mechanistic insights gained and preparation of surface water in silica pores described herein may facilitate the future design of improved “on-water” catalysts.

Citation
Nguyen, D., Casillas, S., Vang, H., Garcia, A., Mizuno, H., Riffe, E. J., … Nguyen, S. C. (2021). Catalytic Mechanism of Interfacial Water in the Cycloaddition of Quadricyclane and Diethyl Azodicarboxylate. The Journal of Physical Chemistry Letters, 3026–3030. doi:10.1021/acs.jpclett.1c00565

Acknowledgements
We thank Dr. Ziliang Mao for the fruitful discussion. This work was supported by the UC Office of the President within the Multicampus Research Programs and Initiatives (M21PL3263) (S.C.N., R.J.S.), Director, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy under Contract No. DEAC02-05CH11231 through the Chemical Sciences Division of the Lawrence Berkeley National Laboratory (R.J.S., H.M.), the King Abdullah University of Science and Technology (E.R.), and the University of California’s Leadership Excellence through Advanced Degrees program (A.G.).

Publisher
American Chemical Society (ACS)

Journal
The Journal of Physical Chemistry Letters

DOI
10.1021/acs.jpclett.1c00565

Additional Links
https://pubs.acs.org/doi/10.1021/acs.jpclett.1c00565

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