Photocatalytic Aerobic Thiol Oxidation with a Self-Sensitized Tellurorhodamine Chromophore

Authors

Luke V. Lutkus, Portland State University
Irving D. Rettig, Portland State UniversityFollow
Kellie S. Davies, The State University of New York
Jacqueline E. Hill, Portland State University
James E. Lohman, Portland State University
Matthew W. Eskew, Portland State University
Michael R. Detty, The State University of New York
Theresa M. McCormick, Portland State UniversityFollow

Sponsor

This research was supported in part by the National Science Foundation (CHE-1566142).

Published In

Organometallics

Document Type

Citation

Publication Date

5-10-2017

Abstract

Aerobic oxidation of thiols to disulfides was achieved photocatalytically using a tellurorhodamine chromophore (9-mesityl-3,6-bis(dimethylamino)telluroxanthylium hexafluorophosphate) as both the sensitizer and catalyst. The proposed mechanism, supported experimentally and computationally with DFT, involves the formation of a tellurorhodamine telluroxide from reaction with water and singlet oxygen generated by irradiation of the tellurorhodamine. The oxidation to the telluroxide is accompanied by the formation of hydrogen peroxide. The telluroxide oxidizes thiols to regenerate the tellurorhodamine and the disulfide plus water. Mechanistically, DFT suggests adding two thiols to the telluroxide with the loss of H2O to give a trigonal-bipyramidal Te(IV), which undergoes concerted loss of disulfide to regenerate 1. Oxidation of thiophenol and 2-naphthalenethiol was complete after 2 h of irradiation with visible light under atmospheric conditions. Oxidation of the electron-poor 2,6-dichlorothiophenol, the sterically bulky tert-butylmercaptan, and aliphatic dodecanethiol was slower. The two aliphatic thiols displayed competing catalyst degradation. The corresponding selenorhodamine chromophore (9-mesityl-3,6-bis(dimethylamino)selenoxanthylium hexafluorophosphate) does not form the corresponding selenoxide under similar conditions and photooxidizes thiophenol and 2-naphthalenethiol much more slowly (≤6% conversion after 2–3 h).

Description

© 2017 American Chemical Society

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.7b00166

Locate the Document

http://dx.doi.org/10.1021/acs.organomet.7b00166

DOI

10.1021/acs.organomet.7b00166

Persistent Identifier

https://archives.pdx.edu/ds/psu/25414

Citation Details

Lutkus, L. V., Irving, H. E., Davies, K. S., Hill, J. E., Lohman, J. E., Eskew, M. W., ... & McCormick, T. M. (2017). Photocatalytic Aerobic Thiol Oxidation with a Self-Sensitized Tellurorhodamine Chromophore. Organometallics, 36(14), 2588-2596.