145571 20260217205604.0 doi 10.1016/j.jorganchem.2024.123385 sideral 140372 ART-2024-140372 eng García-Monforte, Mª Ángeles Universidad de Zaragoza (orcid)0000-0001-7901-1420 Protective effect of the perchlorophenyl group in organophosphorus chemistry 2024 Access copy available to the general public Unrestricted The homoleptic phosphine with the bulky perchlorophenyl group, (C6Cl5)3P (1), exhibits trigonal pyramidal structure (TPY-3), yet considerably flattened: Σ(C–P–C') = 321.0(1)°. Key steric and electronic properties of this simple organophosphorus species have been estimated by calculation. Attending to its characteristic features, 1 can be rated as a deactivated phosphine, where the less-basic P atom is sterically shielded by the bulky C6Cl5 groups. This marked inertness notwithstanding, it has been possible to obtain (under harsh conditions) derivatives with phosphorus in high oxidation state, namely the phosphine oxide (C6Cl5)3PO (2) and the difluorophosphorane (C6Cl5)3PF2 (3). These four- and five-substituted derivatives respectively exhibit trigonal pyramidal (TPY-4) and trigonal bipyramidal (TBPY-5) structures. The Σ(C–P–C') value steadily increases along the series 1–3, according to the referred structural variation. The P–C bond length is, in turn, invariably maintained at about 185 pm regardless of the different oxidation state, the increasing number of substituents around the P atom and the overall geometry. The hypervalent difluorophosphorane (C6Cl5)3PF2 (3) dissociates one of the axial fluorides in the gas phase.Graphical abstract: The perchlorophenyl group, C6Cl5, exerts a protective effect on the P center in a series of related organophosphorus deriva-tives with various geometries (see figure), as established by experimental and theoretical methods.giving rise to the fluorophosphonium cation [(C6Cl5)3PF]+, as detected by mass spectrometry. This cation is identified as a Lewis superacid. info:eu-repo/grantAgreement/ES/DGA/E17-23R info:eu-repo/grantAgreement/ES/MICINN/PID2021-122869NB-I00 info:eu-repo/semantics/openAccess by-nc-nd https://creativecommons.org/licenses/by-nc-nd/4.0/deed.es 2.4 2024 CHEMISTRY, ORGANIC 21 / 57 = 0.368 2024 Q2 T2 CHEMISTRY, INORGANIC & NUCLEAR 22 / 43 = 0.512 2024 Q3 T2 0.385 2024 Biochemistry 2024 Q3 Inorganic Chemistry 2024 Q3 Physical and Theoretical Chemistry 2024 Q3 Organic Chemistry 2024 Q3 Materials Chemistry 2024 Q3 4.1 2024 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Baya, Miguel Universidad de Zaragoza (orcid)0000-0002-2492-625X Martín, Antonio (orcid)0000-0002-4808-574X Menjón, Babil (orcid)0000-0001-9045-5102 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 2010 X Universidad de Zaragoza Dpto. Química Inorgánica Área Técnica. Lab. y Talleres 1022 (2024), 123385 [11 pp.] J. organomet. chem. Journal of Organometallic Chemistry 0022-328X 2243421 http://zaguan.unizar.es/record/145571/files/texto_completo.pdf Versión publicada 2614566 http://zaguan.unizar.es/record/145571/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:145571 articulos driver 2026-02-17-20:45:58 ARTICLE