Structural, vibrational and electronic properties of some tetrel-bonded complexes of the fluorinated methanes methyl fluoride, difluoromethane and fluoroform: an ab initio study

• Published in: Journal of molecular modeling 2022-10, Vol.28 (10), p.294-294, Article 294
• Main Authors: Ramasami, Ponnadurai, Ford, Thomas A.
• Format: Article
• Language: English
• Subjects: Ammonia; Bonding strength; Characterization and Evaluation of Materials; Charge transfer; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Donors (electronic); Fluorination; Hydrogen bonding; Hydrogen chloride; Hydrogen fluoride; Hydrogen sulfide; Molecular Medicine; Molecular orbitals; Original Paper; Phosphines; Theoretical and Computational Chemistry; Trifluoromethane; Vibration mode; Wavelengths
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-022-05285-7

A search has been conducted, by means of ab initio molecular orbital theory, for potential tetrel-bonded complexes formed between the fluorinated methanes methyl fluoride, difluoromethane and fluoroform, and the related hydrides ammonia, water, hydrogen fluoride, phosphine, hydrogen sulphide and hydrogen chloride. Eleven such complexes have been identified, six containing CH 3 F and five CH 2 F 2 . The complexes are typically less strongly bound than their hydrogen-bonded counterparts, and the interaction energies vary in a consistent way with the periodic trend of the electron donors. The intermolecular separations and changes of the relevant intramolecular bond lengths, the wavenumber shifts of the critical vibrational modes and the extents of charge transfer correlate, by and large, with the strengths of interaction. Graphical abstract