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000135325 005__ 20250923084419.0
000135325 0247_ $$2doi$$a10.1002/anie.202403108
000135325 0248_ $$2sideral$$a138584
000135325 037__ $$aART-2024-138584
000135325 041__ $$aeng
000135325 100__ $$0(orcid)0000-0002-0204-7713$$aJoven-Sancho, Daniel
000135325 245__ $$aThe CF<sub>3</sub> Group as a Synthon of the CF<sup>+</sup> Unit in Palladium Chemistry
000135325 260__ $$c2024
000135325 5060_ $$aAccess copy available to the general public$$fUnrestricted
000135325 5203_ $$aThe homoleptic trifluoromethyl‐palladium(II) complex [Pd(CF3)4]2− (1) is shown to be highly active towards amines. Thus, when treated with primary amines RNH2, it readily undergoes aminolysis of one of the CF3 ligands affording the isocyanide complexes [(CF3)3Pd(CNR)]− (R=aryl). In this process the original CF3 group undergoes total defluorination. Interestingly, the reaction of 1 with secondary amines R2NH proceeds with loss of just two F‐substituents, whereby the Fischer‐type fluoroaminocarbene complexes [(CF3)3Pd(CFNR2)]− are formed (R=Et, Ph). The reaction of 1 with diamines affords different [(CF3)3Pd(NHC)]− complexes containing sterically non‐demanding NHC ligands. Representative examples of various topologies are reported based on the common imidazolidin‐2‐ylidene or benzimidazolin‐2‐ylidene rings as well as the expanded‐ring perimidin‐2‐ylidene. This metal‐tailored synthetic route, where a CF3 group acts as a pre‐carbenic unit, is unprecedented in the vast NHC‐chemistry. It takes place under very mild conditions and is envisaged to be extensible to other non‐isolable NHC ligands. The key difluorocarbene intermediate [(CF3)3Pd(CF2)]− is experimentally detected.
000135325 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E17-23R$$9info:eu-repo/grantAgreement/ES/DGA/E47-23R$$9info:eu-repo/grantAgreement/ES/MICINN/PID2021-122869NB-I00$$9info:eu-repo/grantAgreement/ES/MINECO/BES-2016-078732
000135325 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc-nd$$uhttp://creativecommons.org/licenses/by-nc-nd/3.0/es/
000135325 590__ $$a16.9$$b2024
000135325 592__ $$a5.55$$b2024
000135325 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b15 / 239 = 0.063$$c2024$$dQ1$$eT1
000135325 593__ $$aChemistry (miscellaneous)$$c2024$$dQ1
000135325 593__ $$aCatalysis$$c2024$$dQ1
000135325 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000135325 700__ $$0(orcid)0000-0002-2492-625X$$aBaya, Miguel$$uUniversidad de Zaragoza
000135325 700__ $$aMartín, Antonio
000135325 700__ $$0(orcid)0000-0003-3514-2570$$aOrduna, Jesús
000135325 700__ $$0(orcid)0000-0001-9045-5102$$aMenjón, Babil
000135325 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000135325 773__ $$g(2024), e202403108 [7 pp.]$$pAngew. Chem. (Int. ed.)$$tAngewandte Chemie (International ed.)$$x1433-7851
000135325 8564_ $$s1437041$$uhttps://zaguan.unizar.es/record/135325/files/texto_completo.pdf$$yVersión publicada
000135325 8564_ $$s2891806$$uhttps://zaguan.unizar.es/record/135325/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000135325 909CO $$ooai:zaguan.unizar.es:135325$$particulos$$pdriver
000135325 951__ $$a2025-09-22-14:34:46
000135325 980__ $$aARTICLE