INFIQC   05475
INSTITUTO DE INVESTIGACIONES EN FISICO- QUIMICA DE CORDOBA
Unidad Ejecutora - UE
artículos
Título:
Factors Controlling β-Elimination Reactions in Group 10 Complexes
Autor/es:
ERIC DAIANN SOSA CARRIZO; MATTHIAS BICKELHAUPT; ISRAEL FERNÁNDEZ
Revista:
CHEMISTRY-A EUROPEAN JOURNAL
Editorial:
WILEY-V C H VERLAG GMBH
Referencias:
Lugar: Weinheim; Año: 2015 vol. 21 p. 14362 - 14369
ISSN:
0947-6539
Resumen:
Hot Paper: Trends in reactivity of β-chloride and β-hydride elimination reactions involving Group 10 transition-metal complexes have been computationally explored and analyzed in detail by DFT. These reactions do not require the initial formation of a vacant coordination site; they proceed concertedly without a prior ligand-dissociation step. Whereas β-chloride elimination is associated with relatively moderate activation barriers, the high barriers calculated for analogous β-hydride eliminations suggest that the latter process is unfeasible for this type of compounds. This differential behavior is analyzed within the activation strain model, which provides quantitative insight into the physical factors controlling these β-elimination reactions. The effects of the nature of the Group 10 transition metal (Ni, Pd, Pt), as well as the substituents attached to the b-eliminating fragment (R2CCR2X; R, X=H, Cl) on the transformation have also been considered and are rationalized herein.