Structural, Spectroscopic, and Photochemical Investigation of an Octahedral NO-Releasing {RuNO}7 Species

Ru(Me3[9]aneN3)(bpy)(NO)](BF4)2 ([1](BF4)2) was explored by single-crystal X-ray diffractometry, leading to the first crystal structure of an octahedral {RuNO}7 complex. The metal resides on the center of a distorted octahedron, with dN-O and Ru-N-O at 1.177(3) Å and 141.6(2)°, respectively. [1](BF4...

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Autores principales: Osa Codesido, Nicolás, Olabe Iparraguirre, Jose Antonio, Slep, Leonardo Daniel
Publicado: 2016
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v55_n16_p7808_Levin
http://hdl.handle.net/20.500.12110/paper_00201669_v55_n16_p7808_Levin
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_00201669_v55_n16_p7808_Levin
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spelling paper:paper_00201669_v55_n16_p7808_Levin2023-06-08T14:40:44Z Structural, Spectroscopic, and Photochemical Investigation of an Octahedral NO-Releasing {RuNO}7 Species Osa Codesido, Nicolás Olabe Iparraguirre, Jose Antonio Slep, Leonardo Daniel Ru(Me3[9]aneN3)(bpy)(NO)](BF4)2 ([1](BF4)2) was explored by single-crystal X-ray diffractometry, leading to the first crystal structure of an octahedral {RuNO}7 complex. The metal resides on the center of a distorted octahedron, with dN-O and Ru-N-O at 1.177(3) Å and 141.6(2)°, respectively. [1](BF4)2 can be stored indefinitely under argon. Solutions of [1]2+ show no signs of decomposition when protected from air and light. The electron paramagnetic resonance X-band spectrum at 85 K in vitrified acetonitrile (MeCN) shows signals consistent with an S = 1/2 spin state, better described as RuIINO• (g = [2.030, 1.993, 1.880] and A = [11.0, 30.4, 3.9]/10-4 cm-1). In water, the {RuNO}7 species reacts with O2 in a 1:4 stoichiometry. The reaction is first-order in both reactants with k = (1.9 ± 0.2) M-1 s-1 at 25 °C (ΔH‡ = 11.5 ± 0.3 kJ mol-1 ΔS‡ = -189 ± 1 J K-1 mol-1). Solutions of [1]2+ evolve NO when irradiated a 365 nm with øNO = 0.024 and 0.090 mol einstein-1 in H2O and MeCN, respectively. © 2016 American Chemical Society. Fil:Codesido, N.O. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 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. 2016 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v55_n16_p7808_Levin http://hdl.handle.net/20.500.12110/paper_00201669_v55_n16_p7808_Levin
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description Ru(Me3[9]aneN3)(bpy)(NO)](BF4)2 ([1](BF4)2) was explored by single-crystal X-ray diffractometry, leading to the first crystal structure of an octahedral {RuNO}7 complex. The metal resides on the center of a distorted octahedron, with dN-O and Ru-N-O at 1.177(3) Å and 141.6(2)°, respectively. [1](BF4)2 can be stored indefinitely under argon. Solutions of [1]2+ show no signs of decomposition when protected from air and light. The electron paramagnetic resonance X-band spectrum at 85 K in vitrified acetonitrile (MeCN) shows signals consistent with an S = 1/2 spin state, better described as RuIINO• (g = [2.030, 1.993, 1.880] and A = [11.0, 30.4, 3.9]/10-4 cm-1). In water, the {RuNO}7 species reacts with O2 in a 1:4 stoichiometry. The reaction is first-order in both reactants with k = (1.9 ± 0.2) M-1 s-1 at 25 °C (ΔH‡ = 11.5 ± 0.3 kJ mol-1 ΔS‡ = -189 ± 1 J K-1 mol-1). Solutions of [1]2+ evolve NO when irradiated a 365 nm with øNO = 0.024 and 0.090 mol einstein-1 in H2O and MeCN, respectively. © 2016 American Chemical Society.
author Osa Codesido, Nicolás
Olabe Iparraguirre, Jose Antonio
Slep, Leonardo Daniel
spellingShingle Osa Codesido, Nicolás
Olabe Iparraguirre, Jose Antonio
Slep, Leonardo Daniel
Structural, Spectroscopic, and Photochemical Investigation of an Octahedral NO-Releasing {RuNO}7 Species
author_facet Osa Codesido, Nicolás
Olabe Iparraguirre, Jose Antonio
Slep, Leonardo Daniel
author_sort Osa Codesido, Nicolás
title Structural, Spectroscopic, and Photochemical Investigation of an Octahedral NO-Releasing {RuNO}7 Species
title_short Structural, Spectroscopic, and Photochemical Investigation of an Octahedral NO-Releasing {RuNO}7 Species
title_full Structural, Spectroscopic, and Photochemical Investigation of an Octahedral NO-Releasing {RuNO}7 Species
title_fullStr Structural, Spectroscopic, and Photochemical Investigation of an Octahedral NO-Releasing {RuNO}7 Species
title_full_unstemmed Structural, Spectroscopic, and Photochemical Investigation of an Octahedral NO-Releasing {RuNO}7 Species
title_sort structural, spectroscopic, and photochemical investigation of an octahedral no-releasing {runo}7 species
publishDate 2016
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v55_n16_p7808_Levin
http://hdl.handle.net/20.500.12110/paper_00201669_v55_n16_p7808_Levin
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AT olabeiparraguirrejoseantonio structuralspectroscopicandphotochemicalinvestigationofanoctahedralnoreleasingruno7species
AT slepleonardodaniel structuralspectroscopicandphotochemicalinvestigationofanoctahedralnoreleasingruno7species
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