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O ‐versus S ‐protonation in diaryl sulfoxides: A semi‐empirical mo investigation: Comparison with solution studies in superacids
Author(s) -
Laali Kenneth K.,
Houser John J.
Publication year - 1992
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610050505
Subject(s) - protonation , chemistry , sulfonium , heteroatom , onium , computational chemistry , medicinal chemistry , natural bond orbital , crystallography , photochemistry , ion , ring (chemistry) , organic chemistry , density functional theory , salt (chemistry)
The protonation of diphenyl sulfoxide and several substituted diphenyl sulfoxides was probed by the MNDO‐PM3 method to gain a theoretical insight into the experimentally observed preference for stable diphenyl sulfoxonium ion formation ( O ‐protonation) in 1:1 FSO 3 H—SbF 5 (Magic Acid)—SO 2 . In agreement with solution studies, O ‐ protonation is uniformly favored (by ca 17 kcal mol −1 ) over S ‐protonation. The differences in the heats of formation of protonated and unprotonated diphenyl sulfoxides are increased by electron‐withdrawing substituents (F, CF 3 ) and decreased by electron‐donating groups (Me, OMe). Variations in the SO bond length and bond order in the onium ions are compatible with simple resonance arguments and the oxonium/sulfonium character of both the O ‐ and S ‐protonated onium ions. Surprisingly, the O ‐ and S ‐protonated dibenzothiophene S ‐oxides are predicted to have identical energetics as compared with the corresponding protonated diphenyl sulfoxides. On structure optimization dibenzothiophene S ‐oxide itself, if the initial geometry is somewhat twisted, rearranges by ring expansion to give a new heterocycle with lower energy. A rotational barrier study on the parent O ‐protonated diphenyl sulfoxide showed two minima, separated by 1.3 kcal mol −1 , at HOSC dihedral angles of 60° and 240°. The two conformations correspond to syn and anti orientations of the OH proton relative to the aromatic rings, and support the lowtemperature solution observations of the presence of two distinct sulfoxonium ions in solution. The rotational barriers for diphenyl sulfoxonium cation are compared with those of O ‐protonated dimethyl sulfoxide.