150768 20251017144651.0 doi 10.1021/acs.inorgchem.4c04603 sideral 142740 ART-2025-142740 eng Barrena-Espés, Daniel Pentafluoroorthotellurate Uncovered: Theoretical Perspectives on an Extremely Electronegative Group 2025 Access copy available to the general public Unrestricted The pentafluoroorthotellurate group (−OTeF5, teflate) exhibits high electron-withdrawing properties. Indeed, it is often used as a bulky substitute for fluoride due to its high chemical stability and larger size, which reduces its tendency to act as a bridging ligand. These characteristics make it a valuable ligand in synthetic chemistry, facilitating the preparation of molecular structures analogous to polymeric fluoride-based compounds. In this study, we explore the electronic structure of the teflate group by using advanced Quantum Chemical Topology (QCT) methods to better understand its bonding nature and compare its group electronegativity with that of the halogens. For that, we examine XOTeF5 systems (X = F, Cl, Br, I) and decompose X–OTeF5 interactions into classical (ionic) and exchange-correlation (covalent) contributions by using interacting quantum atoms (IQA) energy decomposition scheme. We also conduct a detailed analysis of electron distribution by utilizing the statistical framework of electron distribution functions (EDFs) and examine the electron localization function (ELF), electron density, and reduced density gradient scalar functions, as well as delocalization indices and QTAIM charges. The results show that the electron-withdrawing properties of the teflate group are comparable to those of fluorine, albeit slightly lower. Moreover, its internal bonding is primarily ionic. Additionally, we compare −OTeF5 with other O-donor groups, demonstrating that the electron-withdrawing properties within OEF5 (E = S, Se, Te) systems are nearly identical, and these groups show a higher group electronegativity than OCF3, OC(CF3)3, and OC6F5. info:eu-repo/grantAgreement/ES/DGA/E42-23R info:eu-repo/grantAgreement/ES/MICINN/PID2021-122763NB-I00 info:eu-repo/grantAgreement/ES/UZ/JIUZ-2023-CIE-10 info:eu-repo/semantics/openAccess by https://creativecommons.org/licenses/by/4.0/deed.es info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Martín Pendás, Ángel Riedel, Sebastian Pérez-Bitrián, Alberto Munárriz, Julen Universidad de Zaragoza (orcid)0000-0001-6089-6126 2012 755 Universidad de Zaragoza Dpto. Química Física Área Química Física 64, 2 (2025), 1064-1074 Inorg. chem. Inorganic Chemistry 0020-1669 3408580 http://zaguan.unizar.es/record/150768/files/texto_completo.pdf Versión publicada 2845001 http://zaguan.unizar.es/record/150768/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:150768 articulos driver 2025-10-17-14:36:20 ARTICLE