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

Zierkiewicz, Wiktor; Michalczyk, Mariusz; Scheiner, Steve

doi:10.3390/molecules25030635

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

Wiktor Zierkiewicz

^1,*,

Mariusz Michalczyk

¹ and

Steve Scheiner

^2,*

Faculty of Chemistry, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland

Department of Chemistry and Biochemistry, Utah State University, Logan, UT 84322-0300, USA

Authors to whom correspondence should be addressed.

Academic Editor: Borys Osmialowski

Molecules 2020, 25(3), 635; https://doi.org/10.3390/molecules25030635

Received: 10 January 2020 / Revised: 29 January 2020 / Accepted: 31 January 2020 / Published: 1 February 2020

(This article belongs to the Special Issue Structural Changes in Supramolecular Complexes)

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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 C^α, 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. View Full-Text

Keywords: triel bond; intramolecular triel bond; MP2; MEP; π-hole

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MDPI and ACS Style

Zierkiewicz, W.; Michalczyk, M.; Scheiner, S. Competition between Intra and Intermolecular Triel Bonds. Complexes between Naphthalene Derivatives and Neutral or Anionic Lewis Bases. Molecules 2020, 25, 635. https://doi.org/10.3390/molecules25030635

AMA Style

Zierkiewicz W, Michalczyk M, Scheiner S. Competition between Intra and Intermolecular Triel Bonds. Complexes between Naphthalene Derivatives and Neutral or Anionic Lewis Bases. Molecules. 2020; 25(3):635. https://doi.org/10.3390/molecules25030635

Chicago/Turabian Style

Zierkiewicz, Wiktor, Mariusz Michalczyk, and Steve Scheiner. 2020. "Competition between Intra and Intermolecular Triel Bonds. Complexes between Naphthalene Derivatives and Neutral or Anionic Lewis Bases" Molecules 25, no. 3: 635. https://doi.org/10.3390/molecules25030635

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

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