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

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• 作者：Natalia Levin ; Nicolás Osa Codesido ; Eckhard Bill ; Thomas Weyhermüller ; Ana Paula Segantin Gaspari ; Roberto Santana da Silva ; José A. Olabe ; Leonardo D. Slep
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：August 15, 2016
• 年：2016
• 卷：55
• 期：16
• 页码：7808-7810
• 全文大小：256K
• 年卷期：0
• ISSN：1520-510X

文摘

[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 d_N–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^IINO^• (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 ϕ_NO = 0.024 and 0.090 mol einstein^–1 in H₂O and MeCN, respectively.