000145571 001__ 145571
000145571 005__ 20241108105822.0
000145571 0247_ $$2doi$$a10.1016/j.jorganchem.2024.123385
000145571 0248_ $$2sideral$$a140372
000145571 037__ $$aART-2024-140372
000145571 041__ $$aeng
000145571 100__ $$0(orcid)0000-0001-7901-1420$$aGarcía-Monforte, Mª Ángeles$$uUniversidad de Zaragoza
000145571 245__ $$aProtective effect of the perchlorophenyl group in organophosphorus chemistry
000145571 260__ $$c2024
000145571 5060_ $$aAccess copy available to the general public$$fUnrestricted
000145571 5203_ $$aThe 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.
000145571 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E17-23R$$9info:eu-repo/grantAgreement/ES/MICINN/PID2021-122869NB-I00
000145571 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc-nd$$uhttp://creativecommons.org/licenses/by-nc-nd/3.0/es/
000145571 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000145571 700__ $$0(orcid)0000-0002-2492-625X$$aBaya, Miguel$$uUniversidad de Zaragoza
000145571 700__ $$0(orcid)0000-0002-4808-574X$$aMartín, Antonio
000145571 700__ $$0(orcid)0000-0001-9045-5102$$aMenjón, Babil
000145571 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000145571 7102_ $$12010$$2X$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Técnica. Lab. y Talleres
000145571 773__ $$g1022 (2024), 123385 [11 pp.]$$pJ. organomet. chem.$$tJournal of Organometallic Chemistry$$x0022-328X
000145571 8564_ $$s2243421$$uhttps://zaguan.unizar.es/record/145571/files/texto_completo.pdf$$yVersión publicada
000145571 8564_ $$s2614566$$uhttps://zaguan.unizar.es/record/145571/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000145571 909CO $$ooai:zaguan.unizar.es:145571$$particulos$$pdriver
000145571 951__ $$a2024-11-08-10:38:13
000145571 980__ $$aARTICLE