title: Deeper Insight into the Factors Controlling H2Activation by Geminal Aminoborane-Based Frustrated Lewis Pairs.
abstract: H2activation mediated by geminal aminoborane-based frustrated Lewis pairs (FLPs; R2N-CH2-BR'2) has been computationally explored within the density functional theory framework. It is found that the activation barrier of this process as well as the geometry of the corresponding transition states strongly depend on the nature of the substituents directly attached either to the acidic or the basic centers of the FLPs. The physical factors controlling the whole activation path are quantitatively described in detail by means of the activation strain model of reactivity combined with the energy decomposition analysis method. This methodology suggests a highly orbital-controlled mechanism where the degree of charge transfer cooperativity between the most important donor-acceptor orbital interactions, namely LP(N)→σ*(H2) and σ(H2)→pπ(B), along the reaction coordinate constitutes a suitable indicator of the reaction barrier.
authors.affiliation: Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Av. República 275, Santiago, Chile.|Nucleus Millennium Chemical Processes and Catalysis (CPC), Vicuña Mackenna 4860, Casilla 306, Correo 22, Santiago, Chile.
authors.forename: Diana
authors.identifier: http://orcid.org/0000-0003-4211-7162
authors.initials: D
authors.lastname: Yepes
authors.affiliation: Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Av. República 275, Santiago, Chile.|Nucleus Millennium Chemical Processes and Catalysis (CPC), Vicuña Mackenna 4860, Casilla 306, Correo 22, Santiago, Chile.
authors.forename: Pablo
authors.identifier: http://orcid.org/0000-0002-4055-3553
authors.initials: P
authors.lastname: Jaque
authors.affiliation: Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040, Madrid, Spain.
authors.forename: Israel
authors.identifier: http://orcid.org/0000-0002-0186-9774
authors.initials: I
authors.lastname: Fernández
keywords: aminoboranes; density functional calculations; frustrated Lewis pairs; hydrogen activation; reactivity