title: Factors controlling β-elimination reactions in group 10 metal complexes.
abstract: 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 β-eliminating fragment (R2 CCR2 X; R, X=H, Cl) on the transformation have also been considered and are rationalized herein.
authors.affiliation: Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid (Spain), Fax: (+34) 913944310.|Present address: Departamento de Química Orgánica, Facultad de Ciencias Químicas, INFIQC (CONICET- Universidad Nacional de Córdoba), Medina Allende y Haya de la Torre, X5000HUA, Córdoba (Argentina).
authors.forename: E Daiann
authors.initials: ED
authors.lastname: Sosa Carrizo
authors.affiliation: Department of Theoretical Chemistry, Amsterdam Center for Multiscale Modeling, VU University Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam (The Netherlands). f.m.bickelhaupt@vu.nl.|Institute of Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen (The Netherlands). f.m.bickelhaupt@vu.nl.
authors.forename: F Matthias
authors.initials: FM
authors.lastname: Bickelhaupt
authors.affiliation: Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid (Spain), Fax: (+34) 913944310. israel@quim.ucm.es.
authors.forename: Israel
authors.initials: I
authors.lastname: Fernández
keywords: Group 10 elements; activation strain model; density functional calculations; elimination; reactivity