A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study

The complex cis-[Ru(Lpy)NO]3+ (I) (Lpy = N-(2-methylpyridyl)1,4,8,11-tetraazacyclotetradecane) was prepared by the stoichiometric reaction between Ru(dmso)4Cl2 and Lpy and an excess of NaNO2 in ethanolic medium, followed by acidification of the solution. The diamagnetic species was isolated as its h...

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Detalles Bibliográficos
Publicado: 2007
Materias:
Electronic structure
Nitrosyl
Redox conversion
Ruthenium
Spectroscopy
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_02775387_v26_n16_p4719_DeCandia
http://hdl.handle.net/20.500.12110/paper_02775387_v26_n16_p4719_DeCandia
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_02775387_v26_n16_p4719_DeCandia
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spelling paper:paper_02775387_v26_n16_p4719_DeCandia2023-06-08T15:26:05Z A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study Electronic structure Nitrosyl Redox conversion Ruthenium Spectroscopy The complex cis-[Ru(Lpy)NO]3+ (I) (Lpy = N-(2-methylpyridyl)1,4,8,11-tetraazacyclotetradecane) was prepared by the stoichiometric reaction between Ru(dmso)4Cl2 and Lpy and an excess of NaNO2 in ethanolic medium, followed by acidification of the solution. The diamagnetic species was isolated as its hexafluorophosphate salt, and fully characterized by IR (νNO = 1917 cm-1) and diverse NMR techniques in combination with theoretical computations based on the density functional theory (DFT). The compound displays strong electronic transitions below 300 nm and weak ones in the visible region of the spectrum, all of them solvent insensitive. The reaction of cis-[Ru(Lpy)NO]3+ with OH- generates the strongly colored nitro compound cis-[Ru(Lpy)NO2]+ (II) The {RuNO}6 compound can be interconverted into the one-electron reduced {RuNO}7 species cis-[Ru(Lpy)NO]2+ (III). The reduction process is completely reversible in the cyclic voltammetry timescale with E0 (versus Ag/AgCl, 3 M Cl-) = -0.02 V and 0.18 V in water and acetonitrile, respectively. Controlled potential reduction in both solvents yields to the quantitative formation of III, a process which involves significant changes in the electronic spectroscopy. The {RuNO}7 species proved to be inert against ligand loss, and electrogenerated solutions remained unchanged for several hours if protected from atmospheric oxygen. Electrochemical reoxidation or exposure to air lead to the complete recovery of the starting cis-[Ru(Lpy)NO]3+ material, without signs of secondary reactions. The robustness of the coordination sphere appears as a consequence of the multidentate nature of Lpy. © 2007 Elsevier Ltd. All rights reserved. 2007 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_02775387_v26_n16_p4719_DeCandia http://hdl.handle.net/20.500.12110/paper_02775387_v26_n16_p4719_DeCandia
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Electronic structure
Nitrosyl
Redox conversion
Ruthenium
Spectroscopy
spellingShingle Electronic structure
Nitrosyl
Redox conversion
Ruthenium
Spectroscopy
A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study
topic_facet Electronic structure
Nitrosyl
Redox conversion
Ruthenium
Spectroscopy
description The complex cis-[Ru(Lpy)NO]3+ (I) (Lpy = N-(2-methylpyridyl)1,4,8,11-tetraazacyclotetradecane) was prepared by the stoichiometric reaction between Ru(dmso)4Cl2 and Lpy and an excess of NaNO2 in ethanolic medium, followed by acidification of the solution. The diamagnetic species was isolated as its hexafluorophosphate salt, and fully characterized by IR (νNO = 1917 cm-1) and diverse NMR techniques in combination with theoretical computations based on the density functional theory (DFT). The compound displays strong electronic transitions below 300 nm and weak ones in the visible region of the spectrum, all of them solvent insensitive. The reaction of cis-[Ru(Lpy)NO]3+ with OH- generates the strongly colored nitro compound cis-[Ru(Lpy)NO2]+ (II) The {RuNO}6 compound can be interconverted into the one-electron reduced {RuNO}7 species cis-[Ru(Lpy)NO]2+ (III). The reduction process is completely reversible in the cyclic voltammetry timescale with E0 (versus Ag/AgCl, 3 M Cl-) = -0.02 V and 0.18 V in water and acetonitrile, respectively. Controlled potential reduction in both solvents yields to the quantitative formation of III, a process which involves significant changes in the electronic spectroscopy. The {RuNO}7 species proved to be inert against ligand loss, and electrogenerated solutions remained unchanged for several hours if protected from atmospheric oxygen. Electrochemical reoxidation or exposure to air lead to the complete recovery of the starting cis-[Ru(Lpy)NO]3+ material, without signs of secondary reactions. The robustness of the coordination sphere appears as a consequence of the multidentate nature of Lpy. © 2007 Elsevier Ltd. All rights reserved.
title A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study
title_short A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study
title_full A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study
title_fullStr A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study
title_full_unstemmed A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study
title_sort new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: an experimental and theoretical study
publishDate 2007
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_02775387_v26_n16_p4719_DeCandia
http://hdl.handle.net/20.500.12110/paper_02775387_v26_n16_p4719_DeCandia
_version_ 1768542838357753856

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