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Updated: Dec 31, 2025

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Reversible oxidative-addition and reductive-elimination of thiophene from a titanium complex and its
Alejandra Gómez-Torres1, J Rolando Aguilar-Calderón, Carlos Saucedo
1Department of Chemistry and Biochemistry, University of Texas at El Paso, El Paso, TX 79968, USA. asfortier@utep.edu.
Abstract:
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 hydrodesulphurization of thiophene to give the Ti(iv) sulphide (Ketguan)(ImDippN)Ti(S) (3) and butane.
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