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• W2318174016 endingPage "11095" @default.
• W2318174016 startingPage "11084" @default.
• W2318174016 abstract "Copper complexes of the deprotonated tridentate ligand, N-2-methylthiophenyl-2′-pyridinecarboxamide (HL1), were synthesized and characterized as part of our investigation into the reduction of copper(II) o-nitrito complexes into the related copper nitric oxide complexes and subsequent evolution of NO(g) such as occurs in the enzyme copper nitrite reductase. Our studies afforded the complexes [(L1)CuIICl]n (1), [(L1)CuII(ONO)] (2), [(L1)CuII(H2O)](ClO4)·H2O (3·H2O), [(L1)CuII(CH3OH)](ClO4) (4), [(L1)CuII(CH3CO2)]·H2O (5·H2O), and [Co(Cp)2][(L1)CuI(NO2)(CH3CN)] (6). X-ray crystal structure determinations revealed distorted square-pyramidal coordination geometry around CuII ion in 1–5. Substitution of the H2O of 3 by nitrite quantitatively forms 2, featuring the κ2-O,O binding mode of NO2– to CuII. Reduction of 2 generates two CuI species, one with κ1-O and other with the κ1-N bonded NO2– group. The CuI analogue of 2, compound 6, was synthesized. The FTIR spectrum of 6 reveals the presence of κ1-N bonded NO2–. Constant potential electrolysis corresponding to CuII → CuI reduction of a CH3CN solution of 2 followed by reaction with acids, CH3CO2H or HClO4 generates 5 or 3, and NO(g), identified electrochemically. The isolated CuI complex 6 independently evolves one equivalent of NO(g) upon reaction with acids. Production of NO(g) was confirmed by forming [Co(TPP)NO] in CH2Cl2 (λmax in CH2Cl2: 414 and 536 nm, νNO = 1693 cm–1)." @default.
• W2318174016 created "2016-06-24" @default.
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• W2318174016 creator A5041283276 @default.
• W2318174016 creator A5060517184 @default.
• W2318174016 creator A5076371266 @default.
• W2318174016 date "2013-09-25" @default.
• W2318174016 modified "2023-09-27" @default.
• W2318174016 title "Copper Complexes Relevant to the Catalytic Cycle of Copper Nitrite Reductase: Electrochemical Detection of NO(<i>g</i>) Evolution and Flipping of NO₂ Binding Mode upon Cu^II → Cu^I Reduction" @default.
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• W2318174016 doi "https://doi.org/10.1021/ic401295t" @default.
• W2318174016 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/24066957" @default.
• W2318174016 hasPublicationYear "2013" @default.
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