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Benzylic Complexes of Palladium(II): Bonding modes and Penta- coordination for Steric Relief Martín Ruiz, Blanca Pérez Ortega, Ignacio Albéniz Jiménez, Ana Carmen Chemistry Organometallic Chemistry Palladium Benzyl complexes A large variety of α-(pentafluorophenylmethyl)benzylic palladium complexes with different ligands have been synthesized and char- acterized. Multinuclear NMR spectroscopic data allow to determine the σ-or η3-benzylic nature of the complexes in solution. The adoption of either coordination mode is a function of the number of ligands coordinated to palladium and, remarkably, the presence of bulky phosphines favors the adoption of a bidentate η3-benzylic mode and palladium pentacoordinated complexes. Experimental data and DFT calculations indicate that this five- coordination could alleviate the steric hindrance of two cis bulky phosphines. The benzylic complexes show a rich fluxional behavior that involves both ligand exchange and σ- to η3-benzylic interconversion. Ministerio de Economía, Industria y Competitividad (SGPI, grant CTQ2016-80913-P) 2018-09-09T16:26:19Z 2018-09-09T16:26:19Z 2018 info:eu-repo/semantics/article Organometallics, 2018, Vol. 37, p. 1074-1085 http://uvadoc.uva.es/handle/10324/31462 10.1021/acs.organomet.8b00065 eng https://pubs.acs.org/doi/abs/10.1021/acs.organomet.8b00065 info:eu-repo/semantics/openAccess application/pdf American Chemical Society https://uvadoc.uva.es/bitstream/10324/31462/3/Organometallics%202018%2c%2037%2c%201074%e2%88%921085%20submitted%20manuscript.pdf.jpg Hispana TEXT http://rightsstatements.org/vocab/CNE/1.0/ UVaDOC. Repositorio Documental de la Universidad de Valladolid http://uvadoc.uva.es/handle/10324/31462