Mechanistic Studies of the silyl-Heck Reaction
Date
2012-05
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Publisher
University of Delaware
Abstract
Mechanistic studies of the silyl-Heck reaction were performed. The precatalyst for the reaction was characterized by NMR and X-ray crystallography. NMR experiments were conducted to determine the viability of oxidative addition of the palladium complex across the Si–I bond of iodotrimethylsilane. Variable Temperature NMR experiments were used to confirm the existence of ligand dissociation equilibria between palladium phosphine complexes. VT NMR experiments were also used to determine productive intermediates in the silyl-Heck reaction. A side product formed in the reactions with iodotrimethylsilane was elucidated as a palladium hydride complex. This compound was prepared independently and characterized by NMR and X-ray crystallography. Studies were performed to determine the source of the palladium hydride complex and various sources of hydriodic acid were ruled out. Perdeuterated iodotrimethylsilane was synthesized and used in NMR experiments to rule out the possibility of palladium hydride formation by β-hydride elimination.
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Keywords
silyl-Heck reaction, palladium hydride formation, mechanistic studies, NMR, x-ray crystallography