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

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, Claudio Norberto, Giribet, Claudia Gloria, Contreras, Rubén Horacio
Publicado: 1990
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00222364_v87_n2_p209_Cavasotto
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 paper:paper_00222364_v87_n2_p209_Cavasotto2023-06-08T14:47:35Z 2J(SeSe) couplings in diseleno-substituted alkenylic compounds. A CLOPPA-IPPP analysis Cavasotto, Claudio Norberto Giribet, Claudia Gloria Contreras, Rubén Horacio 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. 1990 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00222364_v87_n2_p209_Cavasotto 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.
author Cavasotto, Claudio Norberto
Giribet, Claudia Gloria
Contreras, Rubén Horacio
spellingShingle Cavasotto, Claudio Norberto
Giribet, Claudia Gloria
Contreras, Rubén Horacio
2J(SeSe) couplings in diseleno-substituted alkenylic compounds. A CLOPPA-IPPP analysis
author_facet Cavasotto, Claudio Norberto
Giribet, Claudia Gloria
Contreras, Rubén Horacio
author_sort Cavasotto, Claudio Norberto
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
publishDate 1990
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00222364_v87_n2_p209_Cavasotto
http://hdl.handle.net/20.500.12110/paper_00222364_v87_n2_p209_Cavasotto
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AT giribetclaudiagloria 2jsesecouplingsindiselenosubstitutedalkenyliccompoundsacloppaipppanalysis
AT contrerasrubenhoracio 2jsesecouplingsindiselenosubstitutedalkenyliccompoundsacloppaipppanalysis
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