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Reversible Oxidative-Addition and Reductive-Elimination of Thiophene from a Titanium Complex and Its Thermally-Induced Hydrodesulfurization Chemistry

preprint
submitted on 18.11.2019 and posted on 27.11.2019 by Alejandra Gomez-Torres, J. Rolando Aguilar-Calderón, Carlos Saucedo, Aldo Jordan, Alejandro J. Metta-Magaña, Balazs Pinter, Skye Fortier

The masked Ti(II) synthon (Ketguan)(η6-ImDippN)Ti (1) oxidatively adds across thiophene to give ring-opened (Ketguan)(ImDippN)Ti[κ2-S(CH)3CH] (2). Complex 2 is photosensitive, and upon exposure to light, reductively eliminates thiophene to regenerate 1 – a rare example of early-metal mediated oxidative-addition/reductive-elimination chemistry. DFT calculations indicate strong titanium π-backdonation to the thiophene π*-orbitals leads to the observed thiophene ring opening across titanium, while a proposed photoinduced LMCT promotes the reverse thiophene elimination from 2. Finally, pressurizing solutions of 2 with H2 (150 psi) at 80 °C leads to the hydrodesulfurization of thiophene to give the Ti(IV) sulfide (Ketguan)(ImDippN)Ti(S) (3) and butane.

Funding

Robert H. Welch Foundation

National Science Foundation

American Chemical Society Petroleum Research Fund

History

Email Address of Submitting Author

asfortier@utep.edu

Institution

University of Texas at El Paso

Country

USA

ORCID For Submitting Author

0000-0002-0502-5229

Declaration of Conflict of Interest

No conflict of interest.

Exports