Interactions of Boranes and Carboranes with Aromatic Systems: CCSD(T) Complete Basis Set Calculations and DFT-SAPT Analysis of Energy Components

0352235 - ÚOCHB 2011 RIV US eng J - Článek v odborném periodiku
Sedlák, Robert - Fanfrlík, Jindřich - Hnyk, Drahomír - Hobza, Pavel - Lepšík, Martin
Interactions of Boranes and Carboranes with Aromatic Systems: CCSD(T) Complete Basis Set Calculations and DFT-SAPT Analysis of Energy Components.
Journal of Physical Chemistry A. Roč. 114, č. 42 (2010), s. 11304-11311. ISSN 1089-5639. E-ISSN 1520-5215
Grant CEP: GA MŠMT LC512; GA MŠMT 1M0508; GA AV ČR IAAX00320901
Výzkumný záměr: CEZ:AV0Z40550506; CEZ:AV0Z40320502
Klíčová slova: noncovalent complex * carborane cage * dispersion
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 2.732, rok: 2010

The CCSD(T)/(CBS) interaction energy for the diborane...benzene complex in a stacking geometry exhibiting a B2H...pi hydrogen bond was calculated to be -4.0 kcal.mol-1. The DFTSAPT/ CBS approach, which reproduce the CCSD(T)/CBS data asserted that the stabilizing component was dispersion, followed by electrostatics. Furthermore, the CB11H12 -...benzene complex exhibited two minima: the first stacked above the plane of the benzene ring with a C-H...pi hydrogen bond and the second planar, in which the carborane cage bound to benzene via five B-H...H-C dihydrogen bonds. The DFT-SAPT/CBS calculations revealed that binding motifs were stabilized by dispersion followed by electrostatic terms, with the planar complex being 1.4 kcal.mol-1 more stable than the stacked one. The dianionic B12H12 2- interacted with benzene only in the planar geometry, similarly as smaller anions do. The stabilization energy was composed of dispersion and slightly smaller electrostatic and induction terms.
Trvalý link: http://hdl.handle.net/11104/0006193