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Group 14 Central Atoms and Halogen Bonding in Different Dielectric Environments: How Germanium Outperforms Silicon

Group 14 Central Atoms and Halogen Bonding in Different Dielectric Environments: How Germanium... The nature of halogen bonding under different dielectric conditions remains underexplored, especially for inorganic systems. The structural and energetic properties of model halogen bonded complexes (R3M−I—NH3 for R=H and F, and M=C, Si, and Ge) are examined computationally for relative permittivities between 1 and 109 using an implicit solvent model. We confirm and assess the exceptionally high maximum potentials at the sigma hole on I (Vs,max) in F3Ge−I relative to cases where M=C or Si. In particular, Ge far outperforms Si in mediating inductive effects. Linear relationships, typically with R2 >0.97, are identified between Vs,max, the full point charge on I in R3M−I, and the interaction energy, and optimized I—N distance in the complexes. An anomalous trend is identified in which, for each M, F3M−I—NH3 becomes less stable as the optimized I—N distance gets shorter in different dielectric environments; it is explained using the F−I—NH3 complex as a reference. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png ChemPlusChem Wiley

Group 14 Central Atoms and Halogen Bonding in Different Dielectric Environments: How Germanium Outperforms Silicon

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References (44)

Publisher
Wiley
Copyright
© 2021 Wiley‐VCH GmbH
eISSN
2192-6506
DOI
10.1002/cplu.202100294
Publisher site
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Abstract

The nature of halogen bonding under different dielectric conditions remains underexplored, especially for inorganic systems. The structural and energetic properties of model halogen bonded complexes (R3M−I—NH3 for R=H and F, and M=C, Si, and Ge) are examined computationally for relative permittivities between 1 and 109 using an implicit solvent model. We confirm and assess the exceptionally high maximum potentials at the sigma hole on I (Vs,max) in F3Ge−I relative to cases where M=C or Si. In particular, Ge far outperforms Si in mediating inductive effects. Linear relationships, typically with R2 >0.97, are identified between Vs,max, the full point charge on I in R3M−I, and the interaction energy, and optimized I—N distance in the complexes. An anomalous trend is identified in which, for each M, F3M−I—NH3 becomes less stable as the optimized I—N distance gets shorter in different dielectric environments; it is explained using the F−I—NH3 complex as a reference.

Journal

ChemPlusChem – Wiley

Published: Oct 1, 2021

Keywords: dielectric environments; geminal polarization; group 14 elements; halogen bonding; sigma holes

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