{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"omics_type":["Unknown"],"volume":["15(30)"],"submitter":["Helou de Oliveira PH"],"pubmed_abstract":["The kinetics of sulfur transfer from titanocene (poly)sulfides (RCp2TiS5, Cp2TiS4CMe2, Cp2Ti(SAr)2, Cp2TiCl(SAr)) to sulfenyl chlorides (S2Cl2, RSCl) have been investigated by a combination of stopped-flow UV-Vis/NMR reaction monitoring, titration assays, numerical kinetic modelling and KS-DFT calculations. The reactions are rapid, proceeding to completion over timescales of milliseconds to minutes, via a sequence of two S-S bond-forming steps (k1, k2). The archetypical polysulfides Cp2TiS5 (1a) and Cp2TiS4C(Me2) (2a) react with disulfur dichloride (S2Cl2) through rate-limiting intermolecular S-S bond formation (k1) followed by a rapid intramolecular cyclization (k2, with k2 ≫ k1 [RSCl]). The monofunctional sulfenyl chlorides (RSCl) studied herein react in two intermolecular S-S bond formi"],"journal":["Chemical science"],"pagination":["11875-11883"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC11290412"],"repository":["biostudies-literature"],"pubmed_title":["Kinetics of sulfur-transfer from titanocene (poly)sulfides to sulfenyl chlorides: rapid metal-assisted concerted substitution."],"pmcid":["PMC11290412"],"pubmed_authors":["West NM","Hembre RT","Garcia-Dominguez A","Lloyd-Jones GC","Al-Afyouni MH","Hua G","Helou de Oliveira PH","Boaler PJ","Penney JM","Woollins JD"],"additional_accession":[]},"is_claimable":false,"name":"Kinetics of sulfur-transfer from titanocene (poly)sulfides to sulfenyl chlorides: rapid metal-assisted concerted substitution.","description":"The kinetics of sulfur transfer from titanocene (poly)sulfides (RCp2TiS5, Cp2TiS4CMe2, Cp2Ti(SAr)2, Cp2TiCl(SAr)) to sulfenyl chlorides (S2Cl2, RSCl) have been investigated by a combination of stopped-flow UV-Vis/NMR reaction monitoring, titration assays, numerical kinetic modelling and KS-DFT calculations. The reactions are rapid, proceeding to completion over timescales of milliseconds to minutes, via a sequence of two S-S bond-forming steps (k1, k2). The archetypical polysulfides Cp2TiS5 (1a) and Cp2TiS4C(Me2) (2a) react with disulfur dichloride (S2Cl2) through rate-limiting intermolecular S-S bond formation (k1) followed by a rapid intramolecular cyclization (k2, with k2 ≫ k1 [RSCl]). The monofunctional sulfenyl chlorides (RSCl) studied herein react in two intermolecular S-S bond formi","dates":{"release":"2024-01-01T00:00:00Z","publication":"2024 Jul","modification":"2025-04-19T20:45:11.431Z","creation":"2025-04-19T20:45:11.431Z"},"accession":"S-EPMC11290412","cross_references":{"pubmed":["39092120"],"doi":["10.1039/d4sc02737j"]}}