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|Type:||Artigo de periódico|
|Title:||Cyclam κ4 To κ3 Ligand Denticity Change Upon Mono-n-substitution With A Carboxypropyl Pendant Arm In A Ruthenium Nitrosyl Complex|
|Abstract:||The complex fac-[Ru(NO)Cl2(κ3N 4,N8,N11(1-carboxypropyl)cyclam)] Cl·H2O (1-carboxypropyl)cyclam = 3-(1,4,8,11- tetraazacyclotetradecan-1-yl)propionic acid) was prepared in a one pot reaction by mixing equimolar amounts of RuNOCl3 and (1-carboxypropyl)cyclam and was characterized by X-ray crystallography, electrospray ionization tandem mass spectrometry (ESI-MS/MS), elemental analysis, NMR, and electronic and vibrational (IR) spectroscopies. fac-[Ru(NO)Cl2(κ 3N4,N8,N11(1-carboxypropyl)cyclam)] Cl·H2O crystallizes in the triclinic, space group P1, No. 2, with unit cell parameters of a = 8.501(1) Å, b = 9.157(1) Å, c = 14.200(1) Å, α = 72.564(5)°, β = 82.512(5)°, γ = 80.308(5)°, and Z = 2. The Ru-N interatomic distance and bond angle in the [Ru-NO] unit are 1.739(2) Å and 167.7(2)°, respectively. ESI-MS/MS shows characteristic dissociation chemistry that initiates by HCl or NO loss. The IR spectrum displays a ν(NO) at 1881 cm-1 indicating a nitrosonium character. The electronic spectrum shows absorptions bands at 264 nm (log ε = 3.27), 404 nm (log ε = 2.53), and 532 nm (log ε = 1.88). 1H and 13C NMR are in agreement with the proposed molecular structure, which shows a very singular architecture where the cyclam ring N (with the carboxypropyl pendant arm) is not coordinated to the ruthenium resulting in a κ3 instead of the expected κ4 denticity. © 2008 American Chemical Society.|
|Citation:||Inorganic Chemistry. , v. 47, n. 10, p. 4118 - 4125, 2008.|
|Appears in Collections:||Unicamp - Artigos e Outros Documentos|
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