Work

Competition between Intra and Intermolecular Triel Bonds. Complexes between Naphthalene Derivatives and Neutral or Anionic Lewis Bases

Year: 2020

Type: article

Abstract: : A TrF2 group (Tr = B, Al, Ga, In, Tl) is placed on one of the α positions of naphthalene, and its ability to engage in a triel bond (TrB) with a weak (NCH) and strong (NC−) nucleophile is assessed by ab initio calculations. As a competitor, an NH2 group is placed on the neighboring Cα, from which point it forms an intramolecular TrB with the TrF2 group. The latter internal TrB reduces the intensity of the π-hole on the Tr atom, decreasing its ability to engage in a second external TrB. The intermolecular TrB is weakened by a factor of about two for the smaller Tr atoms but is less severe for the larger Tl. The external TrB can be quite strong nonetheless; it varies from a minimum of 8 kcal/mol for the weak NCH base, up to as much as 70 kcal/mol for CN−. Likewise, the appearance of an external TrB to a strong base like CN− lessens the ability of the Tr to engage in an internal TrB, to the point where such an intramolecular TrB becomes questionable.

Source: Molecules

DOI: 10.3390/molecules25030635

Authors: Wiktor Zierkiewicz, Mariusz Michalczyk, Steve Scheiner

Institutions: Wrocław University of Science and Technology, Utah State University

Language: English

Topic: Crystallography and molecular interactions

Subfield: Physical and Theoretical Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: gold

Estimated APC paid: $2,112

Funders: Ministerstwo Edukacji i Nauki, Politechnika Wrocławska