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

submitted on 18.11.2019, 17:54 and posted on 27.11.2019, 06:59 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.


Robert H. Welch Foundation

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American Chemical Society Petroleum Research Fund


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University of Texas at El Paso



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No conflict of interest.