Torralvo Martín, HéctorAlbert Mach, JoanAriza Piquer, XavierFont Bardia, Ma. MercedesGarcía Gómez, JordiGranell Sanvicente, Jaime RamónMartínez López, Manuel, 1957-2021-01-262022-01-122021-01-120276-7333https://hdl.handle.net/2445/173399The C-H activation by Pd(II) and Pt(II) compounds of a wide range of imines related to 2-pyridinecarboxaldehyde, ArCH═NCH2(CH2)nPh (Ar = 2-pyridinyl, 2-picolinyl, 2-quinolinyl, n = 0, 1), which can be useful for bond functionalization assisted by bidentate directing groups, has been studied. The results indicate that the presence of two methyl groups at the α-carbon, relative to the imine nitrogen atom, facilitates the metalation. The heterocyclic fragment of the chelating ligand also shows a relevant influence on the full process, the cyclometalated compounds being more easily formed for the 2-picolinyl than for the 2-quinolinyl derivatives, while for the 2-pyridinyl derivatives the reaction is less favored. These effects have been found to be determinant for both palladium and platinum compounds. The preparative results can be explained by a steric enhancement of the metalation process, the reaction being strongly favored when bulky substituents are located in the proximity (α-carbon) of the coordinating nitrogen atoms (with both palladium and platinum). Furthermore, surprisingly the formation of six-membered platinacycles is especially favored. The kinetico-mechanistic studies of the C-H activation reaction, on some equivalent Pd(II) and Pt(II) coordination complexes of the family, have shown that the nature of the d8 metal center plays a determinant role in the reactivity observed. In this respect, the Pt(II) square-planar center has been found to be much more involved in the energetics of the reaction than the Pd(II) equivalent. The full process can be seen as a mechanistic continuum that goes from an electrophilic substitution (Pd(II) centers) to an oxidative addition/reductive elimination sequence (Pt(II) centers). The observation is directly associated with the fact that the Pt(II) center is prone to the existence of oxidatively added Pt(IV) hydrido complexes.15 p.application/pdfeng(c) American Chemical Society , 2021PlatíCompostos orgànicsNitrogenPlatinumOrganic compoundsNitrogeninfo:eu-repo/semantics/article7063242021-01-26info:eu-repo/semantics/openAccess