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“Frustration” of Orbital Interactions in Lewis Base/Lewis Acid Adducts: A Computational Study of H 2 Uptake by Phosphanylboranes R 2 P=BR′ 2
Author(s) -
Nyhlén Jonas,
Privalov Timofei
Publication year - 2009
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200900311
Subject(s) - chemistry , frustrated lewis pair , boron , density functional theory , adduct , reactivity (psychology) , lewis acids and bases , computational chemistry , molecular orbital , perturbation theory (quantum mechanics) , frustration , hydrogen , crystallography , stereochemistry , molecule , organic chemistry , catalysis , quantum mechanics , medicine , physics , alternative medicine , pathology , neuroscience , biology
The reaction of molecular hydrogen with phosphanylboranes R 2 P=BR′ 2 ( 1 ) is systematically studied by means of density functional theory calculations and second order Møller‐Plesset perturbation theory. The potential energy barriers and the exothermicity of H 2 uptake are reported for a series of phosphanylboranes with different electron‐donating and ‐withdrawing groups bound to phosphorus and boron. Systematic molecular orbital analysis reveals that the “frustration” between boron and phosphorus can be increased by modifying the substituents, and thus, atomic orbital interactions could be exploited in order to increase the reactivity of 1 . Additionally, we found a correlation between the potential energy barrier for H 2 uptake and the energy of the HOMO of the P=B complex, which could be relevant for the prediction of the properties of candidate compounds for H 2 activation and therefore useful for the development of such systems. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)