000151634 001__ 151634 000151634 005__ 20250319155217.0 000151634 0247_ $$2doi$$a10.1002/chem.202101859 000151634 0248_ $$2sideral$$a126166 000151634 037__ $$aART-2021-126166 000151634 041__ $$aeng 000151634 100__ $$0(orcid)0000-0002-0204-7713$$aJoven-Sancho D. 000151634 245__ $$aStability of AgIII towards Halides in Organosilver(III) Complexes 000151634 260__ $$c2021 000151634 5060_ $$aAccess copy available to the general public$$fUnrestricted 000151634 5203_ $$aThe involvement of silver in two-electron AgI/AgIII processes is currently emerging. However, the range of stability of the required and uncommon AgIII species is virtually unknown. Here, the stability of AgIII towards the whole set of halide ligands in the organosilver(III) complex frame [(CF3)3AgX]- (X=F, Cl, Br, I, At) is theoretically analyzed. The results obtained depend on a single factor: the nature of X. Even the softest and least electronegative halides (I and At) are found to form reasonably stable AgIII-X bonds. Our estimates were confirmed by experiment. The whole series of nonradiative halide complexes [PPh4][(CF3)3AgX] (X=F, Cl, Br, I) has been experimentally prepared and all its constituents have been isolated in pure form. The pseudohalides [PPh4][(CF3)3AgCN] and [PPh4][(CF3)3Ag(N3)] have also been isolated, the latter being the first silver(III) azido complex. Except for the iodo compound, all the crystal and molecular structures have been established by single-crystal X-ray diffraction methods. The decomposition paths of the [(CF3)3AgX]- entities at the unimolecular level have been examined in the gas phase by multistage mass spectrometry (MSn). The experimental detection of the two series of mixed complexes [CF3AgX]- and [FAgX]- arising from the corresponding parent species [(CF3)3AgX]- demonstrate that the Ag-X bond is particularly robust. Our experimental observations are rationalized with the aid of theoretical methods. Smooth variation with the electronegativity of X is also observed in the thermolyses of bulk samples. The thermal stability in the solid state gradually decreases from X=F (145 °C, dec.) to X=I (78 °C, dec.) The experimentally established compatibility of AgIII with the heaviest halides is of particular relevance to silver-mediated or silver-catalyzed processes. 000151634 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E17-20R$$9info:eu-repo/grantAgreement/ES/MCIU-FEDER/PGC2018-093451-B-I00$$9info:eu-repo/grantAgreement/ES/MICIU-FEDER/PGC2018-094749-B-I00$$9info:eu-repo/grantAgreement/ES/MINECO/BES-2016-078732 000151634 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc-nd$$uhttp://creativecommons.org/licenses/by-nc-nd/3.0/es/ 000151634 590__ $$a5.02$$b2021 000151634 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b64 / 179 = 0.358$$c2021$$dQ2$$eT2 000151634 592__ $$a1.343$$b2021 000151634 593__ $$aChemistry (miscellaneous)$$c2021$$dQ1 000151634 593__ $$aCatalysis$$c2021$$dQ1 000151634 594__ $$a9.1$$b2021 000151634 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion 000151634 700__ $$0(orcid)0000-0002-2492-625X$$aBaya M.$$uUniversidad de Zaragoza 000151634 700__ $$0(orcid)0000-0002-0444-996X$$aFalvello L.R.$$uUniversidad de Zaragoza 000151634 700__ $$0(orcid)0000-0002-4808-574X$$aMartín A. 000151634 700__ $$0(orcid)0000-0003-3514-2570$$aOrduna J. 000151634 700__ $$0(orcid)0000-0001-9045-5102$$aMenjón B. 000151634 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica 000151634 773__ $$g27, 50 (2021), 12796-12806$$pChemistry (Weinh.)$$tChemistry - A European Journal$$x0947-6539 000151634 8564_ $$s3580846$$uhttps://zaguan.unizar.es/record/151634/files/texto_completo.pdf$$yVersión publicada 000151634 8564_ $$s2838274$$uhttps://zaguan.unizar.es/record/151634/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada 000151634 909CO $$ooai:zaguan.unizar.es:151634$$particulos$$pdriver 000151634 951__ $$a2025-03-19-14:19:42 000151634 980__ $$aARTICLE