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:	Waldhör, E., Kaim, W., Olabe, J.A., Slep, L.D., Fiedler, J.
Formato:	JOUR
Acceso en línea:	http://hdl.handle.net/20.500.12110/paper_00201669_v36_n14_p2969_Waldhor
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

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spelling	todo:paper_00201669_v36_n14_p2969_Waldhor2023-10-03T14:16:45Z 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) Waldhör, E. Kaim, W. Olabe, J.A. Slep, L.D. Fiedler, J. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar 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.
format	JOUR
author	Waldhör, E. Kaim, W. Olabe, J.A. Slep, L.D. Fiedler, J.
spellingShingle	Waldhör, E. Kaim, W. Olabe, J.A. Slep, L.D. Fiedler, J. 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	Waldhör, E. Kaim, W. Olabe, J.A. Slep, L.D. Fiedler, J.
author_sort	Waldhör, E.
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)
url	http://hdl.handle.net/20.500.12110/paper_00201669_v36_n14_p2969_Waldhor
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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)

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