Catalytic disproportionation of N-alkylhydroxylamines bound to pentacyanoferrates

The substituted hydroxylamines, CH3N(H)OH (N-methylhydroxylamine) and (CH3)2NOH (N,N-dimethylhydroxylamine), disproportionate catalytically to the corresponding alkylamines and oxidation products, only in the presence of [Fe(CN)5H2O]3−. Substitution kinetic measurements suggest an initial coordinati...

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Publicado: 2009
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14779226_v_n7_p1187_Gutierrez
http://hdl.handle.net/20.500.12110/paper_14779226_v_n7_p1187_Gutierrez
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_14779226_v_n7_p1187_Gutierrez
record_format dspace
spelling paper:paper_14779226_v_n7_p1187_Gutierrez2023-06-08T16:18:19Z Catalytic disproportionation of N-alkylhydroxylamines bound to pentacyanoferrates The substituted hydroxylamines, CH3N(H)OH (N-methylhydroxylamine) and (CH3)2NOH (N,N-dimethylhydroxylamine), disproportionate catalytically to the corresponding alkylamines and oxidation products, only in the presence of [Fe(CN)5H2O]3−. Substitution kinetic measurements suggest an initial coordination step to Fe(ii). Two parallel N- and O-coordination modes are considered with the subsequent formation of Fe(iii), free aminyl (RNCH3) and nitroxide (RN(CH3)O) radicals (R = H, CH3). With CH3N(H)OH, bound nitrosomethane, CH3NO, has been characterized by UV-visible and IR spectroscopies. The mechanism is discussed on the basis of common and differential features with respect to the disproportionation of hydroxylamine catalyzed by the same Fe-fragment. © 2008 The Royal Society of Chemistry. 2009 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14779226_v_n7_p1187_Gutierrez http://hdl.handle.net/20.500.12110/paper_14779226_v_n7_p1187_Gutierrez
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description The substituted hydroxylamines, CH3N(H)OH (N-methylhydroxylamine) and (CH3)2NOH (N,N-dimethylhydroxylamine), disproportionate catalytically to the corresponding alkylamines and oxidation products, only in the presence of [Fe(CN)5H2O]3−. Substitution kinetic measurements suggest an initial coordination step to Fe(ii). Two parallel N- and O-coordination modes are considered with the subsequent formation of Fe(iii), free aminyl (RNCH3) and nitroxide (RN(CH3)O) radicals (R = H, CH3). With CH3N(H)OH, bound nitrosomethane, CH3NO, has been characterized by UV-visible and IR spectroscopies. The mechanism is discussed on the basis of common and differential features with respect to the disproportionation of hydroxylamine catalyzed by the same Fe-fragment. © 2008 The Royal Society of Chemistry.
title Catalytic disproportionation of N-alkylhydroxylamines bound to pentacyanoferrates
spellingShingle Catalytic disproportionation of N-alkylhydroxylamines bound to pentacyanoferrates
title_short Catalytic disproportionation of N-alkylhydroxylamines bound to pentacyanoferrates
title_full Catalytic disproportionation of N-alkylhydroxylamines bound to pentacyanoferrates
title_fullStr Catalytic disproportionation of N-alkylhydroxylamines bound to pentacyanoferrates
title_full_unstemmed Catalytic disproportionation of N-alkylhydroxylamines bound to pentacyanoferrates
title_sort catalytic disproportionation of n-alkylhydroxylamines bound to pentacyanoferrates
publishDate 2009
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14779226_v_n7_p1187_Gutierrez
http://hdl.handle.net/20.500.12110/paper_14779226_v_n7_p1187_Gutierrez
_version_ 1768542566437879808

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