title: Structural, Spectroscopic, and Photochemical Investigation of an Octahedral NO-Releasing {RuNO}(7) Species.
abstract: [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 Ru(II)NO(•) (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 ϕNO = 0.024 and 0.090 mol einstein(-1) in H2O and MeCN, respectively.
authors.affiliation: Universidad de Buenos Aires , Facultad de Ciencias Exactas y Naturales, Departamento de Química Inorgánica, Analítica y Química Física, and INQUIMAE , CONICET, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina.
authors.forename: Natalia
authors.initials: N
authors.lastname: Levin
authors.affiliation: Universidad de Buenos Aires , Facultad de Ciencias Exactas y Naturales, Departamento de Química Inorgánica, Analítica y Química Física, and INQUIMAE , CONICET, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina.
authors.forename: Nicolás Osa
authors.initials: NO
authors.lastname: Codesido
authors.affiliation: Max-Planck Institut für Chemische Energiekonversion , Stiftstraße 34-36, D-45470 Mülheim an der Ruhr, Germany.
authors.forename: Eckhard
authors.initials: E
authors.lastname: Bill
authors.affiliation: Max-Planck Institut für Chemische Energiekonversion , Stiftstraße 34-36, D-45470 Mülheim an der Ruhr, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Weyhermüller
authors.affiliation: Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Departamento de Física e Química, Universidade de São Paulo , Avenida do Café s/n, 14040-903 Ribeirão Preto, São Paolo, Brazil.
authors.forename: Ana Paula
authors.initials: AP
authors.lastname: Segantin Gaspari
authors.affiliation: Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Departamento de Física e Química, Universidade de São Paulo , Avenida do Café s/n, 14040-903 Ribeirão Preto, São Paolo, Brazil.
authors.forename: Roberto Santana
authors.initials: RS
authors.lastname: da Silva
authors.affiliation: Universidad de Buenos Aires , Facultad de Ciencias Exactas y Naturales, Departamento de Química Inorgánica, Analítica y Química Física, and INQUIMAE , CONICET, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina.
authors.forename: José A
authors.initials: JA
authors.lastname: Olabe
authors.affiliation: Universidad de Buenos Aires , Facultad de Ciencias Exactas y Naturales, Departamento de Química Inorgánica, Analítica y Química Física, and INQUIMAE , CONICET, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina.
authors.forename: Leonardo D
authors.initials: LD
authors.lastname: Slep