Experimental Gas-Phase and in Silico Investigation of β‑Methyl Elimination from Cationic Palladium Alkyl Species

Herein we disclose experimental and in silico gas-phase studies of β-methyl and β-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 collis...

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Bibliographic Details
Published inOrganometallics Vol. 34; no. 7; pp. 1301 - 1306
Main Authors Zhugralin, Adil R, Kobylianskii, Ilia J, Chen, Peter
Format Journal Article
LanguageEnglish
Published American Chemical Society 13.04.2015
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Summary:Herein we disclose experimental and in silico gas-phase studies of β-methyl and β-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) β-methyl elimination, (2) Pd–C bond homolysis, or (3) β-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 β-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.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.5b00043