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Type: Artigo de periódico
Title: Effect Of Sulfur Oxidation On The Transmission Mechanism Of4jhh Nmr Coupling Constants In 1,3-dithiane
Author: Gauze G.F.
Basso E.A.
Contreras R.H.
Tormena C.F.
Abstract: Long-range 4JHH couplings in 1,3-dithiane derivatives are rationalized in terms of the effects of hyperconjugative interactions involving the S=0 group. Theoretical and experimental studies of 4JHH couplings were carried out in 1,3-dithiane-l-oxide (2), cw-l,3-dithiane-l,3-dioxide (3), l,3-dithiane-l,l,3-trioxide (4), and 1,3-dithiane-1,1,3,3-tetraoxide (5) compounds. Hyperconjugative interactions were studied with the natural bond orbital, NBO, method. Hyperconjugative interactions involving the LP O, oxygen lone pair and σ*C2-S1 and σ*S1-C6 antibonding orbitals yield an increase of 4JHeq-Heq couplings. Long-range 4JHax-Hax couplings were also observed between hydrogen atoms in axial orientation, which are rationalized as originating in hyperconjugative interactions involving the bonding σC6-h axand antibonding σ*S=O orbitals. The symmetry for orbital interactions is possible only when the S=0 group is in the axial orientation. © 2009 American Chemical Society.
Rights: fechado
Identifier DOI: 10.1021/jp810981z
Date Issue: 2009
Appears in Collections:Unicamp - Artigos e Outros Documentos

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