Effect of sulfur oxidation on the transmission mechanism of4JHH NMR coupling constants in 1,3-dithiane

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-...

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Autores principales: Gauze, G.F., Basso, E.A., Contreras, R.H., Tormena, C.F.
Formato: JOUR
Materias:
3 dioxides
Anti bondings
Antibonding orbitals
Axial orientations
Experimental studies
Hydrogen atoms
Hyperconjugative interactions
Lone pairs
Natural bond orbitals
Nmr couplings
Orbital interactions
Orbitals
Sulfur oxidations
Transmission mechanisms
Hydrogen
Oxygen
Sulfur
Sulfur compounds
Couplings
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_10895639_v113_n11_p2647_Gauze
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling todo:paper_10895639_v113_n11_p2647_Gauze2023-10-03T16:04:37Z Effect of sulfur oxidation on the transmission mechanism of4JHH NMR coupling constants in 1,3-dithiane Gauze, G.F. Basso, E.A. Contreras, R.H. Tormena, C.F. 3 dioxides Anti bondings Antibonding orbitals Axial orientations Experimental studies Hydrogen atoms Hyperconjugative interactions Lone pairs Natural bond orbitals Nmr couplings Orbital interactions Orbitals Sulfur oxidations Transmission mechanisms Hydrogen Oxygen Sulfur Sulfur compounds Couplings 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. Fil:Contreras, R.H. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_10895639_v113_n11_p2647_Gauze
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic 3 dioxides
Anti bondings
Antibonding orbitals
Axial orientations
Experimental studies
Hydrogen atoms
Hyperconjugative interactions
Lone pairs
Natural bond orbitals
Nmr couplings
Orbital interactions
Orbitals
Sulfur oxidations
Transmission mechanisms
Hydrogen
Oxygen
Sulfur
Sulfur compounds
Couplings
spellingShingle 3 dioxides
Anti bondings
Antibonding orbitals
Axial orientations
Experimental studies
Hydrogen atoms
Hyperconjugative interactions
Lone pairs
Natural bond orbitals
Nmr couplings
Orbital interactions
Orbitals
Sulfur oxidations
Transmission mechanisms
Hydrogen
Oxygen
Sulfur
Sulfur compounds
Couplings
Gauze, G.F.
Basso, E.A.
Contreras, R.H.
Tormena, C.F.
Effect of sulfur oxidation on the transmission mechanism of4JHH NMR coupling constants in 1,3-dithiane
topic_facet 3 dioxides
Anti bondings
Antibonding orbitals
Axial orientations
Experimental studies
Hydrogen atoms
Hyperconjugative interactions
Lone pairs
Natural bond orbitals
Nmr couplings
Orbital interactions
Orbitals
Sulfur oxidations
Transmission mechanisms
Hydrogen
Oxygen
Sulfur
Sulfur compounds
Couplings
description 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.
format JOUR
author Gauze, G.F.
Basso, E.A.
Contreras, R.H.
Tormena, C.F.
author_facet Gauze, G.F.
Basso, E.A.
Contreras, R.H.
Tormena, C.F.
author_sort Gauze, G.F.
title Effect of sulfur oxidation on the transmission mechanism of4JHH NMR coupling constants in 1,3-dithiane
title_short Effect of sulfur oxidation on the transmission mechanism of4JHH NMR coupling constants in 1,3-dithiane
title_full Effect of sulfur oxidation on the transmission mechanism of4JHH NMR coupling constants in 1,3-dithiane
title_fullStr Effect of sulfur oxidation on the transmission mechanism of4JHH NMR coupling constants in 1,3-dithiane
title_full_unstemmed Effect of sulfur oxidation on the transmission mechanism of4JHH NMR coupling constants in 1,3-dithiane
title_sort effect of sulfur oxidation on the transmission mechanism of4jhh nmr coupling constants in 1,3-dithiane
url http://hdl.handle.net/20.500.12110/paper_10895639_v113_n11_p2647_Gauze
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