The mpz+/mpz. Pair as Organic Analogue of the NO+/NO. Ligand Redox System (mpz = N-Methylpyrazinium). A Combined Electrochemical and Spectroscopic Study (UV/Vis/NIR, IR, EPR) of Complexes [(mpz)M(CN)5]2-/3- (M = Fe, Ru, Os)

The oxidation and reduction behavior of complexes [(mpz)M(CN)5]2- between the group 8 pentacyanometalates-(II) and the N-methylpyrazinium ion mpz+ was studied using spectroelectrochemical techniques (UV/vis/NIR, IR, EPR) in nonaqueous and, in part, aqueous media. As a further source of information o...

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Autores principales: Olabe Iparraguirre, Jose Antonio, Slep, Leonardo Daniel
Publicado: 1997
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v36_n14_p2969_Waldhor
http://hdl.handle.net/20.500.12110/paper_00201669_v36_n14_p2969_Waldhor
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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_00201669_v36_n14_p2969_Waldhor2023-06-08T14:40:25Z The mpz+/mpz. Pair as Organic Analogue of the NO+/NO. Ligand Redox System (mpz = N-Methylpyrazinium). A Combined Electrochemical and Spectroscopic Study (UV/Vis/NIR, IR, EPR) of Complexes [(mpz)M(CN)5]2-/3- (M = Fe, Ru, Os) Olabe Iparraguirre, Jose Antonio Slep, Leonardo Daniel The oxidation and reduction behavior of complexes [(mpz)M(CN)5]2- between the group 8 pentacyanometalates-(II) and the N-methylpyrazinium ion mpz+ was studied using spectroelectrochemical techniques (UV/vis/NIR, IR, EPR) in nonaqueous and, in part, aqueous media. As a further source of information on the electronic structure, we studied the variable solvatochromism of MLCT absorption bands in the precursor ions [(mpz)M(CN)5]2- The mpz-centered one-electron reduction showed a tendency for concomitant loss of cyanide (EC process) to yield ions [(mpz)M(CN)4]2-, the lability increasing in the order M = Os < < Ru < Fe. In contrast to the EPR spectra obtained from reduction with S2O4 2- in aqueous media, which showed no evidence for close mpz. /metal association, the intra muros electrolysis experiments in DMSO or acetonitrile yielded the following results: The EPR spectrum that was previously assigned to [(mpz)Fe(CN)5]3- is now ascribed to [(mpz)Fe(CN4)]2-. Whereas the dissociatively inert osmium radical complex [(mpz)Os(CN)5]3- is distinguished by a broad EPR signal with a rather large value gisa = 2.0157, the EPR spectrum of [(mpz)Ru(CN)4]3- reveals well-resolved separate coupling with the 99Ru and 101Ru isotopes in natural abundance. Spectroelectrochemistry and reactivity patterns of the complex ions [(mpz)M(CN)5]2- are reminiscent of results for corresponding nitrosyl complexes [(NO)M(CN)5]2-, which suggests that the mpz+/mpz. ligand redox pair can function as an organic analogue of the NO+/NO. redox system. Fil:Olabe, J.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Slep, L.D. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 1997 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v36_n14_p2969_Waldhor http://hdl.handle.net/20.500.12110/paper_00201669_v36_n14_p2969_Waldhor
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 oxidation and reduction behavior of complexes [(mpz)M(CN)5]2- between the group 8 pentacyanometalates-(II) and the N-methylpyrazinium ion mpz+ was studied using spectroelectrochemical techniques (UV/vis/NIR, IR, EPR) in nonaqueous and, in part, aqueous media. As a further source of information on the electronic structure, we studied the variable solvatochromism of MLCT absorption bands in the precursor ions [(mpz)M(CN)5]2- The mpz-centered one-electron reduction showed a tendency for concomitant loss of cyanide (EC process) to yield ions [(mpz)M(CN)4]2-, the lability increasing in the order M = Os < < Ru < Fe. In contrast to the EPR spectra obtained from reduction with S2O4 2- in aqueous media, which showed no evidence for close mpz. /metal association, the intra muros electrolysis experiments in DMSO or acetonitrile yielded the following results: The EPR spectrum that was previously assigned to [(mpz)Fe(CN)5]3- is now ascribed to [(mpz)Fe(CN4)]2-. Whereas the dissociatively inert osmium radical complex [(mpz)Os(CN)5]3- is distinguished by a broad EPR signal with a rather large value gisa = 2.0157, the EPR spectrum of [(mpz)Ru(CN)4]3- reveals well-resolved separate coupling with the 99Ru and 101Ru isotopes in natural abundance. Spectroelectrochemistry and reactivity patterns of the complex ions [(mpz)M(CN)5]2- are reminiscent of results for corresponding nitrosyl complexes [(NO)M(CN)5]2-, which suggests that the mpz+/mpz. ligand redox pair can function as an organic analogue of the NO+/NO. redox system.
author Olabe Iparraguirre, Jose Antonio
Slep, Leonardo Daniel
spellingShingle Olabe Iparraguirre, Jose Antonio
Slep, Leonardo Daniel
The mpz+/mpz. Pair as Organic Analogue of the NO+/NO. Ligand Redox System (mpz = N-Methylpyrazinium). A Combined Electrochemical and Spectroscopic Study (UV/Vis/NIR, IR, EPR) of Complexes [(mpz)M(CN)5]2-/3- (M = Fe, Ru, Os)
author_facet Olabe Iparraguirre, Jose Antonio
Slep, Leonardo Daniel
author_sort Olabe Iparraguirre, Jose Antonio
title The mpz+/mpz. Pair as Organic Analogue of the NO+/NO. Ligand Redox System (mpz = N-Methylpyrazinium). A Combined Electrochemical and Spectroscopic Study (UV/Vis/NIR, IR, EPR) of Complexes [(mpz)M(CN)5]2-/3- (M = Fe, Ru, Os)
title_short The mpz+/mpz. Pair as Organic Analogue of the NO+/NO. Ligand Redox System (mpz = N-Methylpyrazinium). A Combined Electrochemical and Spectroscopic Study (UV/Vis/NIR, IR, EPR) of Complexes [(mpz)M(CN)5]2-/3- (M = Fe, Ru, Os)
title_full The mpz+/mpz. Pair as Organic Analogue of the NO+/NO. Ligand Redox System (mpz = N-Methylpyrazinium). A Combined Electrochemical and Spectroscopic Study (UV/Vis/NIR, IR, EPR) of Complexes [(mpz)M(CN)5]2-/3- (M = Fe, Ru, Os)
title_fullStr The mpz+/mpz. Pair as Organic Analogue of the NO+/NO. Ligand Redox System (mpz = N-Methylpyrazinium). A Combined Electrochemical and Spectroscopic Study (UV/Vis/NIR, IR, EPR) of Complexes [(mpz)M(CN)5]2-/3- (M = Fe, Ru, Os)
title_full_unstemmed The mpz+/mpz. Pair as Organic Analogue of the NO+/NO. Ligand Redox System (mpz = N-Methylpyrazinium). A Combined Electrochemical and Spectroscopic Study (UV/Vis/NIR, IR, EPR) of Complexes [(mpz)M(CN)5]2-/3- (M = Fe, Ru, Os)
title_sort mpz+/mpz. pair as organic analogue of the no+/no. ligand redox system (mpz = n-methylpyrazinium). a combined electrochemical and spectroscopic study (uv/vis/nir, ir, epr) of complexes [(mpz)m(cn)5]2-/3- (m = fe, ru, os)
publishDate 1997
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v36_n14_p2969_Waldhor
http://hdl.handle.net/20.500.12110/paper_00201669_v36_n14_p2969_Waldhor
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