Publication
Title
S···S and S···P chalcogen bonding in solution : a cryospectroscopic study of the complexes of 2,2,4,4-tetrafluoro-1,3-dithietane with dimethyl sulfide and trimethylphosphine
Author
Abstract
n this combined experimental and computational study the complexes formed between 2,2,4,4-tetrafluoro-1,3-dithiethane (C2F4S2) and the Lewis bases dimethyl sulfide (DMS) and trimethylphosphine (TMP) are studied using infrared spectroscopy of solutions in liquid krypton. For C2F4S2 and DMS, ab initio calculations yield two stable chalcogen bonded complex isomers, whereas for C2F4S2 and TMP a single chalcogen bonded complex is predicted. In the infrared spectra of solutions containing C2F4S2 and DMS, evidence for the presence of two complex bands suggesting the simultaneous occurrence of both calculated complex geometries and the lack of rapid interconversion between them is found for several vibrational modes. The average experimental complexation enthalpy for the 1:1 complexes derived from the van t Hoff isochores is -12.3(4) kJ mol-1. The calculated values obtained by combining a complete basis set extrapolation approach and corrections for zero-point vibrational, thermal and solvent influences are -17.3 and -15.8 kJ mol-1 for the first and second geometry, respectively. For the mixtures of C2F4S2 with TMP, single complex bands are found for all vibrational modes, with shifts corresponding well to those of the calculated shifts of the chalcogen bonded complex. The experimental complexation enthalpy for the C2F4S2·TMP complex is -13.0(4) kJ mol-1, whereas the calculated value equals 16.1 kJ mol-1.
Language
English
Source (journal)
New journal of chemistry. - Montrouge
Publication
Montrouge : 2018
ISSN
1144-0546
Volume/pages
42 :13 (2018) , p. 10563-10571
ISI
000436517300017
Full text (Publisher's DOI)
Full text (open access)
UAntwerpen
Faculty/Department
Research group
Project info
4D Protein Structure.
Publication type
Subject
Affiliation
Publications with a UAntwerp address
External links
Web of Science
Record
Identification
Creation 14.05.2018
Last edited 06.09.2021
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