title: Understanding the Oxidative Addition of σ-Bonds to Group 13 Compounds.
abstract: The oxidative addition reaction of X-H σ-bonds to Group 13 (E=Al, Ga, In) containing compounds has been computationally explored within the density functional theory framework. These reactions, which proceed concertedly involving the E(I) →E(III) oxidation, are exothermic and associated with relatively low activation barriers. In addition, the following trends in reactivity are found: (i) the activation barriers are lower for the X-H bonds involving the heavier element in the same group (ΔE(≠) : C>Si; N>P; O>S), (ii) the process becomes kinetically more favorable in going from left to right in the same period (ΔE(≠) : C>N>O; Si≈P>S), and (iii) the activation barrier systematically increases when heavier Group 13 elements are involved in the transformation (ΔE(≠) : Al<Ga<In). These reactivity trends are analyzed and quantitatively rationalized in detail by means of the activation-strain model of reactivity in combination with the energy decomposition analysis method.
authors.affiliation: Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense, 28040, Madrid, Spain.
authors.forename: Yago
authors.identifier: http://orcid.org/0000-0001-6245-1665
authors.initials: Y
authors.lastname: García-Rodeja
authors.affiliation: Department of Theoretical Chemistry, Amsterdam Center for Multiscale Modeling, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands. f.m.bickelhaupt@vu.nl.|Institute of Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525 AJ, Nijmegen, The Netherlands. f.m.bickelhaupt@vu.nl.
authors.forename: F Matthias
authors.identifier: http://orcid.org/0000-0003-4655-7747
authors.initials: FM
authors.lastname: Bickelhaupt
authors.affiliation: Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense, 28040, Madrid, Spain. israel@quim.ucm.es.
authors.forename: Israel
authors.identifier: http://orcid.org/0000-0002-0186-9774
authors.initials: I
authors.lastname: Fernández
keywords: Group 13; activation strain; density functional calculations; oxidative addition; reactivity