An investigation of the kinetics of the reaction between titanocene pentasulfide and sulfenyl chloride[1] leading to the formation of the S7 allotrope of sulfur was accompanied by supporting DFT calculations which led to the conclusion that of five possible mechanisms for the reaction, the most probable corresponded to a variant of the concerted σ-bond metathesis (Scheme 1, Mechanism IV, R = Cl). Here we take a closer look at the DFT predictions from the point of view of the impact of continuum solvation on the calculated mechanism.
References
- P.H. Helou de Oliveira, P.J. Boaler, G. Hua, N.M. West, R.T. Hembre, J.M. Penney, M.H. Al-Afyouni, J.D. Woollins, A. García-Domínguez, and G.C. Lloyd-Jones, "Kinetics of sulfur-transfer from titanocene (poly)sulfides to sulfenyl chlorides: rapid metal-assisted concerted substitution", Chemical Science, vol. 15, pp. 11875-11883, 2024. https://doi.org/10.1039/d4sc02737j