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RESEARCH PRODUCT
Unveiling the Sulfur–Sulfur Bridge: Accurate Structural and Energetic Characterization of a Homochalcogen Intermolecular Bond
Lorenzo SpadaDaniel A. ObenchainMarco MendolicchioVincenzo BaroneSergio RampinoSven HerbersPeter KrausJens-uwe GrabowJürgen GaussCristina PuzzariniSilvia AlessandriniNicola Tasinatosubject
Materials sciencechemistry.chemical_element02 engineering and technologybond analysi010402 general chemistry01 natural sciencesQuantum chemistryCatalysisCatalysibond analysisquantum chemistrysymbols.namesakeChalcogenrotational spectroscopyVan der Waals radiusPhysics::Chemical PhysicsAstrophysics::Galaxy Astrophysicsbond analysis; energy and charge decomposition models; quantum chemistry; rotational spectroscopy; semi-experimental equilibrium structure; Catalysis; Chemistry (all)energy and charge decomposition model010405 organic chemistryIntermolecular forceChemistry (all)General MedicineGeneral Chemistryenergy and charge decomposition modelssemi-experimental equilibrium structure021001 nanoscience & nanotechnologySulfur0104 chemical scienceschemistryChemical physicssymbolsRotational spectroscopy0210 nano-technologyDispersion (chemistry)Natural bond orbitaldescription
open 12 si MIUR “PRIN 2015” funds (Grant Number 2015F59J3R) 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 backbone of the molecular complex has been determined, which is characterized by a S⋅⋅⋅S distance (2.947(3) Å) well below the sum of van der Waals radii. embargoed_20191010 Obenchain, Daniel A.; Spada, Lorenzo; Alessandrini, Silvia; Rampino, Sergio; Herbers, Sven; Tasinato, Nicola; Mendolicchio, Marco; Kraus, Peter; Gauss, Jürgen; Puzzarini, Cristina; Grabow, Jens-Uwe*; Barone, Vincenzo Obenchain, Daniel A.; Spada, Lorenzo; Alessandrini, Silvia; Rampino, Sergio; Herbers, Sven; Tasinato, Nicola; Mendolicchio, Marco; Kraus, Peter; Gauss, Jürgen; Puzzarini, Cristina; Grabow, Jens-Uwe*; Barone, Vincenzo
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2018-10-31 |