Reduction of the NO+ ligand in the pentacyanonitrosylosmate(II) ion

The reversible reduction of [Os(CN)5(NO)]2-, the osmium analog of the nitroprusside ion, has been studied by spectroelectrochemical techniques (IR, UV-Vis, EPR). The strong shift of the nitrosyl stretching band from 1850 to 1560 cm-1 (in acetonitrile) already indicates nitrosyl ligand-centered reduc...

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Autores principales: Baumann, F., Kaim, W., M. Baraldo, L., Slep, L.D., Olabe, J.A., Fiedler, J.
Formato: JOUR
Materias:
Cyanide complexes
EPR
Nitrosyl complexes
Osmium complexes
Spectroelectrochemistry
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_00201693_v285_n1_p129_Baumann
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling todo:paper_00201693_v285_n1_p129_Baumann2023-10-03T14:17:15Z Reduction of the NO+ ligand in the pentacyanonitrosylosmate(II) ion Baumann, F. Kaim, W. M. Baraldo, L. Slep, L.D. Olabe, J.A. Fiedler, J. Cyanide complexes EPR Nitrosyl complexes Osmium complexes Spectroelectrochemistry The reversible reduction of [Os(CN)5(NO)]2-, the osmium analog of the nitroprusside ion, has been studied by spectroelectrochemical techniques (IR, UV-Vis, EPR). The strong shift of the nitrosyl stretching band from 1850 to 1560 cm-1 (in acetonitrile) already indicates nitrosyl ligand-centered reduction in comparison to the smaller shifts for the cyanide frequencies (2140 → 2080 cm-1). Remarkably, the g factor analysis (g|| = 2.017, g⊥ = 2.003) for electrogenerated [Os(CN)5(NO)]3- does not reflect any effect from the 5d element osmium with its high spin-orbit coupling constant; only the need to apply helium temperatures for EPR signal observation indicates the presence of a heavy transition metal. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00201693_v285_n1_p129_Baumann
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Cyanide complexes
EPR
Nitrosyl complexes
Osmium complexes
Spectroelectrochemistry
spellingShingle Cyanide complexes
EPR
Nitrosyl complexes
Osmium complexes
Spectroelectrochemistry
Baumann, F.
Kaim, W.
M. Baraldo, L.
Slep, L.D.
Olabe, J.A.
Fiedler, J.
Reduction of the NO+ ligand in the pentacyanonitrosylosmate(II) ion
topic_facet Cyanide complexes
EPR
Nitrosyl complexes
Osmium complexes
Spectroelectrochemistry
description The reversible reduction of [Os(CN)5(NO)]2-, the osmium analog of the nitroprusside ion, has been studied by spectroelectrochemical techniques (IR, UV-Vis, EPR). The strong shift of the nitrosyl stretching band from 1850 to 1560 cm-1 (in acetonitrile) already indicates nitrosyl ligand-centered reduction in comparison to the smaller shifts for the cyanide frequencies (2140 → 2080 cm-1). Remarkably, the g factor analysis (g|| = 2.017, g⊥ = 2.003) for electrogenerated [Os(CN)5(NO)]3- does not reflect any effect from the 5d element osmium with its high spin-orbit coupling constant; only the need to apply helium temperatures for EPR signal observation indicates the presence of a heavy transition metal.
format JOUR
author Baumann, F.
Kaim, W.
M. Baraldo, L.
Slep, L.D.
Olabe, J.A.
Fiedler, J.
author_facet Baumann, F.
Kaim, W.
M. Baraldo, L.
Slep, L.D.
Olabe, J.A.
Fiedler, J.
author_sort Baumann, F.
title Reduction of the NO+ ligand in the pentacyanonitrosylosmate(II) ion
title_short Reduction of the NO+ ligand in the pentacyanonitrosylosmate(II) ion
title_full Reduction of the NO+ ligand in the pentacyanonitrosylosmate(II) ion
title_fullStr Reduction of the NO+ ligand in the pentacyanonitrosylosmate(II) ion
title_full_unstemmed Reduction of the NO+ ligand in the pentacyanonitrosylosmate(II) ion
title_sort reduction of the no+ ligand in the pentacyanonitrosylosmate(ii) ion
url http://hdl.handle.net/20.500.12110/paper_00201693_v285_n1_p129_Baumann
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