Publications by authors named "Jordan Rio"
Article Synopsis
- Mechanistic studies using density functional theory (DFT) for organic and organometallic reactions in solution are now common and complement experimental work.
- The initial challenge in this approach is selecting the right DFT functional for accurate energy barrier calculations, with evaluations made on both non-empirical (like PBE and PBE0) and empirical functionals (like BLYP and B3LYP).
- General findings indicate that non-empirical functionals tend to perform better than empirical ones, with PBE0 and PBE0-DH yielding the most accurate results for energy barriers, while adding GD3-BJ dispersion correction doesn't improve accuracy.
Controlling and understanding the Cu-catalyzed homocoupling reaction is crucial to prompt the development of efficient Cu-catalyzed cross-coupling reactions. The presence of a coordinating base (hydroxide and methoxide) enables the B-to-Cu(II) transmetalation from aryl boronic acid to CuCl in methanol, through the formation of mixed Cu-(μ-OH)-B intermediates. A second B-to-Cu transmetalation to form bis-aryl Cu(II) complexes is disfavored.
View Article and Find Full Text PDFHalide salts facilitate the oxidative addition of organic halides to Pd(0). This phenomenon originates from a combination of anionic, cationic, and Pd-Pd cooperative effects. Exhaustive computational exploration at the density functional theory level of the complexes obtained from [Pd(PPh)] and a salt (NMeCl or LiCl) showed that chlorides promote phosphine release, leading to a mixture of mononuclear and dinuclear Pd(0) complexes.
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