1431223-25-4Relevant articles and documents
A detailed study of acetate-assisted C-H activation at palladium(IV) centers
Maleckis, Ansis,Kampf, Jeff W.,Sanford, Melanie S.
, p. 6618 - 6625 (2013/06/05)
This report describes a detailed investigation of acetate-assisted C-H activation at PdIV centers supported by the tris(2-pyridyl)methane (Py3CH) ligand. Mechanistic information about this transformation has been obtained through the following: (i) extensive one- and two-dimensional NMR analysis, (ii) reactivity studies of a series of substituted analogues, and (iii) isotope effect studies. These experiments all suggest that C-H activation at [(Py3CH)PdIV(biphenyl)Cl2]+ occurs via a multistep process involving chloride-to-acetate ligand exchange followed by conformational and configurational isomerization and then C-H cleavage. The data also suggest that C-H cleavage proceeds via an acetate-assisted mechanism with the carboxylate likely serving as an intramolecular base. The viability of acetate-assisted C-H activation at high valent palladium has important implications for the design and optimization of catalytic processes involving this transformation as a key step.