Document Type

Article

Journal/Book Title

ChemPhysChem

Publication Date

9-17-2018

Publisher

Wiley-VCH Verlag GmbH & Co. KGaA

Volume

19

Issue

22

First Page

1

Last Page

32

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)3paired 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.

Comments

This is the peer reviewed version of the following article: Michalczyk, M., Zierkiewicz, W., Scheiner, S. I. (2018). Triel-Bonded Complexes between TrR3 (Tr=B, Al, Ga; R=H, F, Cl, Br, CH3) and Pyrazine. ChemPhysChem, 19(22), 3122-3133. https://onlinelibrary.wiley.com/doi/abs/10.1002/cphc.201800774, which has been published in final form at https://doi.org/10.1002/cphc.201800774. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.

Included in

Chemistry Commons

Share

COinS
 
 

To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.