Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 48, Pages 15822-15826Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201810637
Keywords
body analysis; energy and charge decomposition models quantum chemistry; rotational spectroscopy; semi-experimental equilibrium structure
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Funding
- Alexander von Humboldt Foundation
- Land Niedersachsen
- DFG
- MIUR PRIN 2015 funds [2015F59J3R]
- University of Bologna (RFO funds)
- Scuola Normale Superiore [SNS18_B_TASINATO]
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By combining rotational spectroscopy in supersonic expansion with the capability of state-of-the-art quantum-chemical computations in accurately determining structural and energetic properties, the genuine nature of a sulfur-sulfur chalcogen bond between dimethyl sulfide and sulfur dioxide has been unveiled in a gas-jet environment free from collision, solvent and matrix perturbations. A SAPT analysis pointed out that electrostatic S....S interactions play the dominant role in determining the stability of the complex, largely overcoming dispersion and C-H.....O hydrogen-bond contributions. Indeed, in agreement with the analysis of the quadrupole-coupling constants and of the methyl internal rotation barrier, the NBO and NOCV/CD approaches show a marked charge transfer between the sulfur atoms. Based on the assignment of the rotational spectra for 7 isotopologues, an accurate semi-experimental equilibrium structure for the heavy-atom back-bone of the molecular complex has been determined which is characterized by a S.....S distance (2.947(3)) well below the sum of van der Waals radii.
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