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Structural and Energetic Properties of H3N–MX3R Complexes
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  • James Phillips,
  • Anna Ley,
  • Patrick Treacy,
  • Benjamin Wahl,
  • Brittany Zehner,
  • Kelling Donald,
  • Samuel Gillespie
James Phillips
University of Wisconsin Eau Claire
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Anna Ley
University of Wisconsin Eau Claire
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Patrick Treacy
University of Wisconsin Eau Claire
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Benjamin Wahl
University of Wisconsin Eau Claire
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Brittany Zehner
University of Wisconsin Eau Claire
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Kelling Donald
University of Richmond
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Samuel Gillespie
University of Richmond
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Abstract

We have explored the structural and energetic properties of a series of RMX3–NH3 (M=Si, Ge; X=F, Cl; R=CH3, C6H5) complexes using density functional theory and low-temperature infrared spectroscopy. In the minimum-energy structures, the NH3 binds axially to a halogen, while the organic group resides in equatorial site about the metal. Remarkably, the primary mode of interaction in several of these systems seems to be hydrogen bonding (C-H–N), rather than a tetrel N-M interaction. This is particularly clear for the RMCl3–NH3 complexes, and analyses of the charge distributions of the acid fragment corroborate this assessment. We also identified a set of metastable geometries in which the ammonia binds axial to the organic substituent. Acid fragment charge analysis also provide a clear rationale as to why these configurations are less stable than their R-equatorial counterparts. In matrix-IR experiments, we see clear evidence of the minimum-energy form of CH3SiCl3–NH3, but analogous results for CH3GeCl3–NH3 are less conclusive. Computational scans of the M-N distance potentials for CH3SiCl3–NH3 and CH3GeCl3–NH3, both in the gas phase and bulk dielectric media reveal a great deal of anharmonicity, and a propensity for condensed-phase structural change.

Peer review status:ACCEPTED

15 May 2020Submitted to International Journal of Quantum Chemistry
15 May 2020Submission Checks Completed
15 May 2020Assigned to Editor
27 May 2020Reviewer(s) Assigned
04 Jun 2020Review(s) Completed, Editorial Evaluation Pending
05 Jun 2020Editorial Decision: Revise Minor
17 Jun 20201st Revision Received
18 Jun 2020Submission Checks Completed
18 Jun 2020Assigned to Editor
22 Jun 2020Reviewer(s) Assigned
22 Jun 2020Review(s) Completed, Editorial Evaluation Pending
22 Jun 2020Editorial Decision: Accept