2J(SeSe) couplings in diseleno-substituted alkenylic compounds. A CLOPPA-IPPP analysis

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A CLOPPA-IPPP analysis of 2J(SeSe) couplings in two cyclic diseleno-substituted alkenylic compounds is performed. The total FC, PSO, DSO, and SD components of these couplings are evaluated within the RPA-INDO approximation, and total values are compared to the experimental values. The PSO interactio...

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Autores principales: Cavasotto, C.N., Giribet, C.G., de Azúa, M.C.R., Contreras, R.H., Pérez, J.E.
Formato: JOUR
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_00222364_v87_n2_p209_Cavasotto
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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_00222364_v87_n2_p209_Cavasotto2023-10-03T14:28:47Z 2J(SeSe) couplings in diseleno-substituted alkenylic compounds. A CLOPPA-IPPP analysis Cavasotto, C.N. Giribet, C.G. de Azúa, M.C.R. Contreras, R.H. Pérez, J.E. A CLOPPA-IPPP analysis of 2J(SeSe) couplings in two cyclic diseleno-substituted alkenylic compounds is performed. The total FC, PSO, DSO, and SD components of these couplings are evaluated within the RPA-INDO approximation, and total values are compared to the experimental values. The PSO interaction yields large values in both cases. Particularly, it is the dominant interaction in the cyclic plane compound. For this case, an analysis of the main transmission mechanisms of the SO term is performed in terms of localized molecular orbitals (LMOs) representing chemical functions. It is seen that the coupling is mainly transmitted by the occupied and vacant LMOs associated with the Se atoms. The influence of the π-type Se lone pairs is negligible, while the inplane Se lone pairs play an important role. Additivity of pathways is also analyzed: a "direct" and an "indirect" nonadditivity of paths are defined. A high direct nonadditivity is observed. A curious influence of the occupied π vinylic MO in the indirect nonadditivity is shown. Even though it is known that in several geminal couplings the DSO term yields an important contribution, it has a value of only about 10-2 Hz in the present case. © 1990. Fil:Cavasotto, C.N. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Giribet, C.G. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 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_00222364_v87_n2_p209_Cavasotto
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description A CLOPPA-IPPP analysis of 2J(SeSe) couplings in two cyclic diseleno-substituted alkenylic compounds is performed. The total FC, PSO, DSO, and SD components of these couplings are evaluated within the RPA-INDO approximation, and total values are compared to the experimental values. The PSO interaction yields large values in both cases. Particularly, it is the dominant interaction in the cyclic plane compound. For this case, an analysis of the main transmission mechanisms of the SO term is performed in terms of localized molecular orbitals (LMOs) representing chemical functions. It is seen that the coupling is mainly transmitted by the occupied and vacant LMOs associated with the Se atoms. The influence of the π-type Se lone pairs is negligible, while the inplane Se lone pairs play an important role. Additivity of pathways is also analyzed: a "direct" and an "indirect" nonadditivity of paths are defined. A high direct nonadditivity is observed. A curious influence of the occupied π vinylic MO in the indirect nonadditivity is shown. Even though it is known that in several geminal couplings the DSO term yields an important contribution, it has a value of only about 10-2 Hz in the present case. © 1990.
format JOUR
author Cavasotto, C.N.
Giribet, C.G.
de Azúa, M.C.R.
Contreras, R.H.
Pérez, J.E.
spellingShingle Cavasotto, C.N.
Giribet, C.G.
de Azúa, M.C.R.
Contreras, R.H.
Pérez, J.E.
2J(SeSe) couplings in diseleno-substituted alkenylic compounds. A CLOPPA-IPPP analysis
author_facet Cavasotto, C.N.
Giribet, C.G.
de Azúa, M.C.R.
Contreras, R.H.
Pérez, J.E.
author_sort Cavasotto, C.N.
title 2J(SeSe) couplings in diseleno-substituted alkenylic compounds. A CLOPPA-IPPP analysis
title_short 2J(SeSe) couplings in diseleno-substituted alkenylic compounds. A CLOPPA-IPPP analysis
title_full 2J(SeSe) couplings in diseleno-substituted alkenylic compounds. A CLOPPA-IPPP analysis
title_fullStr 2J(SeSe) couplings in diseleno-substituted alkenylic compounds. A CLOPPA-IPPP analysis
title_full_unstemmed 2J(SeSe) couplings in diseleno-substituted alkenylic compounds. A CLOPPA-IPPP analysis
title_sort 2j(sese) couplings in diseleno-substituted alkenylic compounds. a cloppa-ippp analysis
url http://hdl.handle.net/20.500.12110/paper_00222364_v87_n2_p209_Cavasotto
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