Journal of Molecular Modeling

, Volume 14, Issue 8, pp 689–697 | Cite as

Why are dimethyl sulfoxide and dimethyl sulfone such good solvents?

  • Timothy Clark
  • Jane S. Murray
  • Pat Lane
  • Peter PolitzerEmail author
Original Paper


We have carried out B3PW91 and MP2-FC computational studies of dimethyl sulfoxide, (CH3)2SO, and dimethyl sulfone, (CH3)2SO2. The objective was to establish quantitatively the basis for their high polarities and boiling points, and their strong solvent powers for a variety of solutes. Natural bond order analyses show that the sulfur–oxygen linkages are not double bonds, as widely believed, but rather are coordinate covalent single S+→O bonds. The calculated electrostatic potentials on the molecular surfaces reveal several strongly positive and negative sites (the former including σ-holes on the sulfurs) through which a variety of simultaneous intermolecular electrostatic interactions can occur. A series of examples is given. In terms of these features the striking properties of dimethyl sulfoxide and dimethyl sulfone, their large dipole moments and dielectric constants, their high boiling points and why they are such good solvents, can readily be understood.


Dimers of dimethyl sulfoxide (DMSO; left) and dimethyl sulfone (DMSO2; right) showing O S—O -hole bonding and C H—O hydrogen bonding. Sulfur atoms are yellow, oxygens are red, carbons are gray and hydrogens are white


Dimethyl sulfoxide Dimethyl sulfone Electrostatic potentials σ-Hole bonding Noncovalent interactions 



This work was supported in part by the Deutsche Forschungsgemeinschaft as part of SFB583 Redox-active Metal Complexes: Control of Reactivity via Molecular Architecture.


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Copyright information

© Springer-Verlag 2008

Authors and Affiliations

  • Timothy Clark
    • 1
    • 2
  • Jane S. Murray
    • 3
    • 4
  • Pat Lane
    • 3
  • Peter Politzer
    • 3
    • 4
    Email author
  1. 1.Computer-Chemie-CentrumFriedrich-Alexander-Universität Erlangen-NürnbergErlangenGermany
  2. 2.Interdiscplinary Center for Molecular MaterialsFriedrich-Alexander-Universität Erlangen-NürnbergErlangenGermany
  3. 3.Department of ChemistryUniversity of New OrleansNew OrleansUSA
  4. 4.Department of ChemistryCleveland State UniversityClevelandUSA

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