Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 22, Issue 52, Pages 18801-18809Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201603889
Keywords
aminoboranes; density functional calculations; frustrated Lewis pairs; hydrogen activation; reactivity
Categories
Funding
- FONDECYT [1140340, 3150249]
- Spanish MINECO-FEDER [CTQ2013-44303-P, CTQ2014-51912-REDC, CTQ2016-78205-P]
Ask authors/readers for more resources
H-2 activation mediated by geminal aminoboranebased 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)->sigma*(H-2) and sigma(H-2)-> p(pi)(B), along the reaction coordinate constitutes a suitable indicator of the reaction barrier.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available