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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todo:paper_00201669_v55_n16_p7808_Levin2023-10-03T14:17:09Z Structural, Spectroscopic, and Photochemical Investigation of an Octahedral NO-Releasing {RuNO}7 Species Levin, N. Codesido, N.O. Bill, E. Weyhermüller, T. Segantin Gaspari, A.P. Da Silva, R.S. Olabe, J.A. Slep, L.D. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar 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. |
| format |
JOUR |
| author |
Levin, N. Codesido, N.O. Bill, E. Weyhermüller, T. Segantin Gaspari, A.P. Da Silva, R.S. Olabe, J.A. Slep, L.D. |
| spellingShingle |
Levin, N. Codesido, N.O. Bill, E. Weyhermüller, T. Segantin Gaspari, A.P. Da Silva, R.S. Olabe, J.A. Slep, L.D. Structural, Spectroscopic, and Photochemical Investigation of an Octahedral NO-Releasing {RuNO}7 Species |
| author_facet |
Levin, N. Codesido, N.O. Bill, E. Weyhermüller, T. Segantin Gaspari, A.P. Da Silva, R.S. Olabe, J.A. Slep, L.D. |
| author_sort |
Levin, N. |
| 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 |
| url |
http://hdl.handle.net/20.500.12110/paper_00201669_v55_n16_p7808_Levin |
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1782024105638232064 |