Theoretical calculations of chemical interactions. Part 6. An MNDO study of the intermediates involved in CO insertion into lithium-nitrogen bonds in lithium dialkylamides

Carbon monoxide insertion into Li-N bonds in lithium dialkylamides provides a useful synthetic method not only for substituted formamides but also for highly functionalized compounds such as substituted glyoxylamides and tartronamides. The high instability of the intermediates involved precludes dir...

Descripción completa

Guardado en:
Detalles Bibliográficos
Autores principales: Nudelman, N.S., Perez, D.G.
Formato: JOUR
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_1472779X_v_n8_p931_Nudelman
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id todo:paper_1472779X_v_n8_p931_Nudelman
record_format dspace
spelling todo:paper_1472779X_v_n8_p931_Nudelman2023-10-03T16:18:07Z Theoretical calculations of chemical interactions. Part 6. An MNDO study of the intermediates involved in CO insertion into lithium-nitrogen bonds in lithium dialkylamides Nudelman, N.S. Perez, D.G. Carbon monoxide insertion into Li-N bonds in lithium dialkylamides provides a useful synthetic method not only for substituted formamides but also for highly functionalized compounds such as substituted glyoxylamides and tartronamides. The high instability of the intermediates involved precludes direct independent determination of the various steps involved but theoretical calculations provide a way of predicting their feasibility. Both INDO and MNDO procedures have been used but the MNDO method has been found to be more appropriate for this study. The geometries and energies of the proposed intermediates have been calculated as well as the equilibrium positions for several acid-base equilibria and the energy changes involved in the different steps. An estimation of the solvent interaction with the charged intermediates has allowed a prediction of the temperature effect which is consistent with the observed experimental results. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_1472779X_v_n8_p931_Nudelman
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description Carbon monoxide insertion into Li-N bonds in lithium dialkylamides provides a useful synthetic method not only for substituted formamides but also for highly functionalized compounds such as substituted glyoxylamides and tartronamides. The high instability of the intermediates involved precludes direct independent determination of the various steps involved but theoretical calculations provide a way of predicting their feasibility. Both INDO and MNDO procedures have been used but the MNDO method has been found to be more appropriate for this study. The geometries and energies of the proposed intermediates have been calculated as well as the equilibrium positions for several acid-base equilibria and the energy changes involved in the different steps. An estimation of the solvent interaction with the charged intermediates has allowed a prediction of the temperature effect which is consistent with the observed experimental results.
format JOUR
author Nudelman, N.S.
Perez, D.G.
spellingShingle Nudelman, N.S.
Perez, D.G.
Theoretical calculations of chemical interactions. Part 6. An MNDO study of the intermediates involved in CO insertion into lithium-nitrogen bonds in lithium dialkylamides
author_facet Nudelman, N.S.
Perez, D.G.
author_sort Nudelman, N.S.
title Theoretical calculations of chemical interactions. Part 6. An MNDO study of the intermediates involved in CO insertion into lithium-nitrogen bonds in lithium dialkylamides
title_short Theoretical calculations of chemical interactions. Part 6. An MNDO study of the intermediates involved in CO insertion into lithium-nitrogen bonds in lithium dialkylamides
title_full Theoretical calculations of chemical interactions. Part 6. An MNDO study of the intermediates involved in CO insertion into lithium-nitrogen bonds in lithium dialkylamides
title_fullStr Theoretical calculations of chemical interactions. Part 6. An MNDO study of the intermediates involved in CO insertion into lithium-nitrogen bonds in lithium dialkylamides
title_full_unstemmed Theoretical calculations of chemical interactions. Part 6. An MNDO study of the intermediates involved in CO insertion into lithium-nitrogen bonds in lithium dialkylamides
title_sort theoretical calculations of chemical interactions. part 6. an mndo study of the intermediates involved in co insertion into lithium-nitrogen bonds in lithium dialkylamides
url http://hdl.handle.net/20.500.12110/paper_1472779X_v_n8_p931_Nudelman
work_keys_str_mv AT nudelmanns theoreticalcalculationsofchemicalinteractionspart6anmndostudyoftheintermediatesinvolvedincoinsertionintolithiumnitrogenbondsinlithiumdialkylamides
AT perezdg theoreticalcalculationsofchemicalinteractionspart6anmndostudyoftheintermediatesinvolvedincoinsertionintolithiumnitrogenbondsinlithiumdialkylamides
_version_ 1807324201246261248

Ejemplares similares