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Herein we disclose experimental and in silico gas-phase studies of beta-methyl and beta-hydride elimination from cationic diphosphine palladium(II) neopentyl and isobutyl complexes. In particular, we have determined activation barriers for these transformations through mass-spectrometric threshold collision-induced dissociation (T-CID) studies. These systems can undergo at least one of the several competitive processes: (1) beta-methyl elimination, (2) Pd-C bond homolysis, or (3) beta-hydride elimination. We also confirm that qualitative trends in the branching ratios between these processes depend on the diphosphine bite angle, whereas electronic modifications of phosphine electron-donating ability have no significant effect on the barriers for beta-methyl elimination within the experimental error. The full reaction manifold has been investigated with density functional theory (DFT) and affords a valuable experimental benchmark for types of organometallic transformations described herein. (Chemical Equation Presented).
Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data. Recommanded Product: 95464-05-4, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 95464-05-4, in my other articles.
Reference：
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method