Data Documentation for the supplemetary material of the article "Photochemical halogen-bonding assisted generation of vinyl and sulfur-centered radicals: stereoselective catalyst-free C(sp2)–S bond forming reactions". Chemical Science, doi: 10.1039/D2SC05556B General Information Supplementary information for the article "Photochemical halogen-bonding assisted generation of vinyl and sulfur-centered radicals: stereoselective catalyst-free C(sp2)–S bond forming reactions" Chemical Science: DOI: 10.1039/D2SC05556B. The data are contained in a word .docx file with the chemdraw and NMR data embebed. NMR data in mestrenova format can be retrieved from the file. Name of dataset: Supplementary Information revised Name of data files in data set: Supplementary Information revised.doc Dataset language: English Date the data set was last modified: 16-11-2022 Funder: Financial support of this work by an FICYT (Principality of Asturias) “Margarita Salas J´ oven” postdoctoral grant to M. P. (AYUD/2021/58397) is gratefully acknowledged. We wish to thank Prof. Carlos Vald´ es for his assistance with the DFT calculations and helpful discussions during the development of this work. How to cite data: Fernández Piedra, H.; Plaza, M. Photochemical halogen-bonding assisted generation of vinyl and sulfur-centered radicals: stereoselective catalyst-free C(sp2)–S bond forming reactions. Chem. Sci. 2024, 14, 650-657. https://doi.org/10.1039/D2SC05556B Methodology for data collection: Data collector(s): Helena Fernández Piedra Date of data collection: 2023 Person to contact with questions: Manuel Plaza Data entry: 13-05-2025 Software (including version #) used to prepare data set: MSword, Chemdraw22.2, MestreNova 14 Data processing that was performed: NMR FIDs were processed with MestreNova, copied and pasted in the Word document Variables File Overview Supplementary Information revised: a .docx file containing all the experimental and NMR data,: NMR mestrenova files can be retrieved oorm the document.