Theoretical characterization of stable η1-N2O-, η2-N2O-, η1-N2-, and η2-N2-bound species: Intermediates in the addition reactions of nitrogen hydrides with the pentacyanonitrosylferrate(II) ion

The addition of nitrogen hydrides (hydrazine, hydroxylamine, ammonia, azide) to the pentacyanonitrosylferrate(II) ion has been analyzed by means of density functional calculations, focusing on the identification of stable intermediates along the reaction paths. Initial reversible adduct formation an...

Descripción completa

Guardado en:
Detalles Bibliográficos
Autor principal: Olabe Iparraguirre, Jose Antonio
Publicado: 2003
Materias:
ammonia
azide
ferrous ion
hydrazine
hydroxylamine
nitrogen
nitrous oxide
pentacyanonitrosylferrate(ii)
unclassified drug
article
calculation
density functional calculation
isomer
molecular stability
reaction analysis
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v42_n16_p4873_Olabe
http://hdl.handle.net/20.500.12110/paper_00201669_v42_n16_p4873_Olabe
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_00201669_v42_n16_p4873_Olabe
record_format dspace
spelling paper:paper_00201669_v42_n16_p4873_Olabe2023-06-08T14:40:32Z Theoretical characterization of stable η1-N2O-, η2-N2O-, η1-N2-, and η2-N2-bound species: Intermediates in the addition reactions of nitrogen hydrides with the pentacyanonitrosylferrate(II) ion Olabe Iparraguirre, Jose Antonio ammonia azide ferrous ion hydrazine hydroxylamine nitrogen nitrous oxide pentacyanonitrosylferrate(ii) unclassified drug article calculation density functional calculation isomer molecular stability reaction analysis The addition of nitrogen hydrides (hydrazine, hydroxylamine, ammonia, azide) to the pentacyanonitrosylferrate(II) ion has been analyzed by means of density functional calculations, focusing on the identification of stable intermediates along the reaction paths. Initial reversible adduct formation and further decomposition lead to the η1- and η2-linkage isomers of N2O and N2, depending on the nucleophile. The intermediates (adducts and gas-releasing precursors) have been characterized at the B3LYP/6-31G** level of theory through the calculation of their structural and spectroscopic properties, modeling the solvent by means of a continuous approach. The η2-N2O isomer is formed at an initial stage of adduct decompositions with the hydrazine and azide adducts. Further conversion to the η1-N2O isomer is followed by Fe-N2O dissociation. Only the η1-N2O isomer is predicted for the reaction with hydroxylamine, revealing a kinetically controlled N2O formation. η1-N2 and η2-N2 isomers are also predicted as stable species. Fil:Olabe, J.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2003 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v42_n16_p4873_Olabe http://hdl.handle.net/20.500.12110/paper_00201669_v42_n16_p4873_Olabe
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic ammonia
azide
ferrous ion
hydrazine
hydroxylamine
nitrogen
nitrous oxide
pentacyanonitrosylferrate(ii)
unclassified drug
article
calculation
density functional calculation
isomer
molecular stability
reaction analysis
spellingShingle ammonia
azide
ferrous ion
hydrazine
hydroxylamine
nitrogen
nitrous oxide
pentacyanonitrosylferrate(ii)
unclassified drug
article
calculation
density functional calculation
isomer
molecular stability
reaction analysis
Olabe Iparraguirre, Jose Antonio
Theoretical characterization of stable η1-N2O-, η2-N2O-, η1-N2-, and η2-N2-bound species: Intermediates in the addition reactions of nitrogen hydrides with the pentacyanonitrosylferrate(II) ion
topic_facet ammonia
azide
ferrous ion
hydrazine
hydroxylamine
nitrogen
nitrous oxide
pentacyanonitrosylferrate(ii)
unclassified drug
article
calculation
density functional calculation
isomer
molecular stability
reaction analysis
description The addition of nitrogen hydrides (hydrazine, hydroxylamine, ammonia, azide) to the pentacyanonitrosylferrate(II) ion has been analyzed by means of density functional calculations, focusing on the identification of stable intermediates along the reaction paths. Initial reversible adduct formation and further decomposition lead to the η1- and η2-linkage isomers of N2O and N2, depending on the nucleophile. The intermediates (adducts and gas-releasing precursors) have been characterized at the B3LYP/6-31G** level of theory through the calculation of their structural and spectroscopic properties, modeling the solvent by means of a continuous approach. The η2-N2O isomer is formed at an initial stage of adduct decompositions with the hydrazine and azide adducts. Further conversion to the η1-N2O isomer is followed by Fe-N2O dissociation. Only the η1-N2O isomer is predicted for the reaction with hydroxylamine, revealing a kinetically controlled N2O formation. η1-N2 and η2-N2 isomers are also predicted as stable species.
author Olabe Iparraguirre, Jose Antonio
author_facet Olabe Iparraguirre, Jose Antonio
author_sort Olabe Iparraguirre, Jose Antonio
title Theoretical characterization of stable η1-N2O-, η2-N2O-, η1-N2-, and η2-N2-bound species: Intermediates in the addition reactions of nitrogen hydrides with the pentacyanonitrosylferrate(II) ion
title_short Theoretical characterization of stable η1-N2O-, η2-N2O-, η1-N2-, and η2-N2-bound species: Intermediates in the addition reactions of nitrogen hydrides with the pentacyanonitrosylferrate(II) ion
title_full Theoretical characterization of stable η1-N2O-, η2-N2O-, η1-N2-, and η2-N2-bound species: Intermediates in the addition reactions of nitrogen hydrides with the pentacyanonitrosylferrate(II) ion
title_fullStr Theoretical characterization of stable η1-N2O-, η2-N2O-, η1-N2-, and η2-N2-bound species: Intermediates in the addition reactions of nitrogen hydrides with the pentacyanonitrosylferrate(II) ion
title_full_unstemmed Theoretical characterization of stable η1-N2O-, η2-N2O-, η1-N2-, and η2-N2-bound species: Intermediates in the addition reactions of nitrogen hydrides with the pentacyanonitrosylferrate(II) ion
title_sort theoretical characterization of stable η1-n2o-, η2-n2o-, η1-n2-, and η2-n2-bound species: intermediates in the addition reactions of nitrogen hydrides with the pentacyanonitrosylferrate(ii) ion
publishDate 2003
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v42_n16_p4873_Olabe
http://hdl.handle.net/20.500.12110/paper_00201669_v42_n16_p4873_Olabe
work_keys_str_mv AT olabeiparraguirrejoseantonio theoreticalcharacterizationofstableē1n2oē2n2oē1n2andē2n2boundspeciesintermediatesintheadditionreactionsofnitrogenhydrideswiththepentacyanonitrosylferrateiiion
_version_ 1768542674818695168

Ejemplares similares