The kinetic order of an interfacial Diels-Alder reaction depends on the environment of the immobilized dienophile

Angewandte Chemie - International Edition

Volumn 39, Issue 11, 2000, Pages 1943-1946

  Yousaf, Muhammad N ^a   Chan, Eugene W L ^a   Mrksich, Milan ^a  

^a UNIVERSITY OF CHICAGO   (United States)

Author keywords

Cycloadditions; Electrochemistry; Interfaces; Kinetics; Monolayers

Indexed keywords

CYCLOPENTADIENE DERIVATIVE; HYDROQUINONE;

ARTICLE; CHEMICAL REACTION KINETICS; CYCLIC POTENTIOMETRY; OXIDATION; REDUCTION;

EID: 0034595815     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3773(20000602)39:11<1943::AID-ANIE1943>3.0.CO;2-#     Document Type: Article

References (20)

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10. o is the fraction of alkanethiolates in the monolayer that present quinone groups, and was determined by integrating the waves in the cyclic voltammograms.
11. Cyclic voltammetry was performed with a Bioanalytical Systems CV-50W potentiostat using a cell with the gold/SAM as the working electrode, a platinum wire as the counter electrode, and Ag/AgCl as the reference electrode.
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15. Ellipsometric measurements were made with a Gaertner model L116S Research Type manual thin-film ellipsometer operating at 632.8 nm (He-Ne laser) and an angle of incidence of 70°. A value of 1.45 was used for the average refractive index of the SAM. The SAM presenting quinone groups had an average thickness of 21.4 ± 0.7 Å. After reaction with 1-hexyl-cyclopentadiene the SAM had a thickness of 34.4 ± 0.8 Å. Both values are consistent with the proposed structures.
16. For an example of previous work that used cyclic voltammetry to measure the rate of an interfacial reaction, see M. Maskus, H. Abruna, Langmuir 1996, 12, 4455.
17. A monolayer presenting only quinone groups gave heterogeneous kinetic behavior in that the reactivity of the quinone groups was dependent on the extent of reaction. This contrasting behavior gives evidence that the mixed monolayers used in this work were not phase-separated.
18. This model is analogous, though not identical, to the formalism of Langmuir - Hinshelwood. For a review, see W. H. Weinberg, Acc. Chem. Res. 1996, 29, 479.
19. For examples of the characterization of interfacial reactions, see a) K. L. Sun, R. C. Thomas, R. M. Crooks, A. J. Ricco, J. Am. Chem. Soc. 1991. 113, 8550;
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