Triel‐Bonded Complexes between TrR3 (Tr=B, Al, Ga; R=H, F, Cl, Br, CH3) and Pyrazine. Issue 22 (10th October 2018)

• Record Type: Journal Article
• Authors: Michalczyk, Mariusz; Zierkiewicz, Wiktor; Scheiner, Steve
• Is Part Of: Chemphyschem. Volume 19:Issue 22(2018)
• Page Start: 3122
• Page End: 3133
• Publication Date: 2018-10-10
• Subjects: ab initio calculations -- complexes -- molecular modelling -- π-holes, pyrazine; Chemistry, Physical and theoretical -- Periodicals; 541.05
• DOI: 10.1002/cphc.201800774
• Languages: English
• ISSNs: 1439-4235

Abstract

Abstract: Complexes between TrR3 (Tr=B, Al, Ga; R=H, F, Cl, Br, CH3 ) molecules and pyrazine have been characterized at the MP2 and CCSD(T) levels of theory. The adducts can be grouped according to the type of molecular arrangement. The first situation places the Tr atom in the plane of the pyrazine ring and contains a triel bond to the N lone pair. For the boron complexes the orbital interaction energy is almost equal to the electrostatic component, while the former is only half the latter for Tr=Al and Ga. The two monomers are stacked above one another in the second configuration, which depends to a greater degree upon orbital interaction and dispersion. The former complexes are more strongly bonded than the latter. Interaction energies (Eint ) for the stronger complexes vary between −50 and −20 kcal/mol for BBr3 and Ga(CH3 )3 paired respectively with pyrazine. Eint is much smaller for the stacked configurations, ranging from −8 for GaF3 to −1.4 kcal/mol for BF3 . The value of the maximum of the electrostatic potential correlates poorly with Eint, attributed in part to monomer distortions upon complexation. Abstract : TrR3 molecules (where Tr=B, Al, Ga, and R=H, F, Cl, Br, CH3 ) engage in two types of triel‐bonded complexes with pyrazine. In much stronger bonded complexes, Tr is located in the plane of the pyrazine ring, interacting directly with an N lone pair. The two monomers are stacked above one another in weaker complexes, which are dependent upon orbital interaction and dispersion.