Sulfoxides feature relatively short S-O distances. In DMSO, the S-O distance is 1.531 Å. The sulfur center is pyramidal; the sum of the angles at sulfur is about 306°.
Sulfoxides are generally represented with the structural formula R-S(=O)-R', where R and R' are organic groups. The bond between the sulfur and oxygen atoms is intermediate of a dative bond and a polarized double bond. The double-bond resonance form implies 10 electrons around sulfur (10-S-3 in N-X-L notation). The double-bond character of the S-O bond may be accounted for by donation of electron density into C-S antibonding orbitals ("no-bond" resonance forms in valence-bond language). Nevertheless, due to its simplicity and lack of ambiguity, the IUPAC recommends use of the expanded octet double-bond structure to depict sulfoxides, rather than the dipolar structure or structures that invoke "no-bond" resonance contributors. The S-O interaction has an electrostatic aspect, resulting in significant dipolar character, with negative charge centered on oxygen.
A lone pair of electrons resides on the sulfur atom, giving it tetrahedral electron-pair geometry and trigonal pyramidal shape (steric number 4 with one lone pair; see VSEPR theory). When the two organic residues are dissimilar, the sulfur is a chiral center, for example, in methyl phenyl sulfoxide. The energy barrier required to invert this stereocenter is sufficiently high that sulfoxides are optically stable near room temperature. That is, the rate of racemization is slow at room temperature. The enthalpy of activation for racemization is in the range 35 - 42 kcal/mol and the corresponding entropy of activation is -8 - +4 cal/mol-K. The barriers are lower for allylic and benzylic substituents.
Both aryl sulfinyl chlorides and diaryl sulfoxides can be also prepared from arenes through reaction with thionyl chloride in the presence of Lewis acid catalysts such as BiCl3, Bi(OTf)3, LiClO4, or NaClO4.
Deoxygenation and oxygenation
Sulfoxides undergo deoxygenation to give sulfides. Typically metal complexes are used to catalyze the reaction, using hydrosilanes as the stoichiometric reductant. The deoxygenation of dimethylsulfoxide is catalyzed by DMSO reductase, a molybdoenzyme:
OSMe2 + 2e- + 2 H+ -> SMe2 + H2O
Sulfoxides can be oxidized to sulfones using peroxide:
OSR2 + H2O2 -> O2SR2 + H2O
The ?-CH groups of alkyl sulfoxides are susceptible to deprotonation by strong bases, such as sodium hydride:
Pyrolysis of alkyl methyl sulfoxides results in loss of methylsulfenic acid, giving the vinyl derivative:
CH3S(O)CH2CH2R -> CH3SOH + CH2=CHR
cis-RuCl2(dmso)4, a representative metal complex of a sulfoxide. Three DMSO ligands are S-bonded to Ru, one is O-bonded.
Sulfoxides, especially DMSO, form coordination complexes with transition metals. Depending on the hard-soft properties of the metal, the sulfoxide binds through either the sulfur or the oxygen atom. The latter is particularly common.
The sulfoxide functional group occurs in several drugs. Notable is esomeprazole, the optically pure form of the proton-pump inhibitor omeprazole. Another commercially important sulfoxides include armodafinil.
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