ChemPhysChem

Volume 15, Issue 14 p. 2985-2993

Article

Boron and other Triel Lewis Acid Centers: From Hypovalency to Hypervalency

Corresponding Author

Prof. Dr. Sławomir J. Grabowski

[email protected]

Kimika Fakultatea, Euskal Herriko Unibertsitatea UPV/EHU and Donostia International Physics Center (DIPC), P.K. 1072, 20080 Donostia (Spain)

IKERBASQUE, Basque Foundation for Science, 48011 Bilbao (Spain)

Kimika Fakultatea, Euskal Herriko Unibertsitatea UPV/EHU and Donostia International Physics Center (DIPC), P.K. 1072, 20080 Donostia (Spain)Search for more papers by this author

Prof. Dr. Sławomir J. Grabowski,

Corresponding Author

Prof. Dr. Sławomir J. Grabowski

[email protected]

Kimika Fakultatea, Euskal Herriko Unibertsitatea UPV/EHU and Donostia International Physics Center (DIPC), P.K. 1072, 20080 Donostia (Spain)

IKERBASQUE, Basque Foundation for Science, 48011 Bilbao (Spain)

Kimika Fakultatea, Euskal Herriko Unibertsitatea UPV/EHU and Donostia International Physics Center (DIPC), P.K. 1072, 20080 Donostia (Spain)Search for more papers by this author

First published: 18 September 2014

https://doi.org/10.1002/cphc.201402344

Citations: 134

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Graphical Abstract

Changing valency: The interaction of a ZF₃ trigonal structure (Z=B, Al, Ga, In, Tl) with a single HCN or N₂ ligand may lead to a tetrahedral structure with a tetravalent triel atom, whereas interaction of ZF₃ with two ligands results in a trigonal bipyramidal structure with a pentacoordinate Z atom. Of all the triel centers, the boron center forms complexes with the weakest interactions.

Abstract

MP2/aug-cc-pVTZ calculations were performed on triel trifluorides, ZF₃ (Z=B, Al, Ga, In, Tl), and their complexes with N₂ and HCN species, which are acting as Lewis bases. Interaction of the ZF₃ trigonal structure with a single HCN or N₂ ligand may lead to a tetrahedral structure with the tetravalent triel atom, whereas interaction of ZF₃ with two ligands results in a trigonal bipyramidal structure with a pentacoordinate Z atom. Consequently, the Z atom in ZF₃ compounds suffers from electron deficiency (hypovalency), it obeys the octet rule in ZF₃–NCH and ZF₃–N₂ moieties, and it may be considered as a hypervalent center in complexes of ZF₃ with two ligands. Much weaker interactions are observed for the boron complexes than for the other triel systems. This is because of the lower acidity of the B center relative to that of the other triel centers, and it may be the result of a stronger backbonding effect for BF₃ than for the other triel trifluorides. Interactions in aluminum complexes are characterized by meaningful electrostatic contributions, whereas for gallium complexes, the most important electron charge shift is observed as a result of complexation. Analysis of the geometry of the triel complexes and of the Z⋅⋅⋅N interactions (triel bonds) in these complexes is based on ab initio calculations as well as on the quantum theory of atoms in molecules and the natural bond orbitals method.

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Volume15, Issue14

October 6, 2014

Pages 2985-2993

Boron and other Triel Lewis Acid Centers: From Hypovalency to Hypervalency

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Abstract

Supporting Information

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Citing Literature

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Boron and other Triel Lewis Acid Centers: From Hypovalency to Hypervalency

Graphical Abstract

Abstract

Supporting Information

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