Cyclam [kappa] super(4) to [kappa] super(3) Ligand Denticity Change Upon Mono-N-Substitution with a Carboxypropyl Pendant Arm in a Ruthenium Nitrosyl Complex

The complex fac-[Ru(NO)Cl sub(2)([kappa] super(3)N super(4), N super(8), N super(11)(1-carboxypropyl)cyclam)]Cl[middot]H sub(2)O (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 RuNOCl sub(3) and (1-c...

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Bibliographic Details
Published in:Inorganic chemistry 2008-05, Vol.47 (10), p.4118-4125
Main Authors: Doro, Fabio G, Castellano, Eduardo E, Moraes, Luiz A B, Eberlin, Marcos N, Tfouni, Elia
Format: Article
Language:English
Subjects:
Architecture
Electronics
Ionization
Jewelry
Molecular structure
Nuclear magnetic resonance
Ruthenium
Unit cell
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Summary:The complex fac-[Ru(NO)Cl sub(2)([kappa] super(3)N super(4), N super(8), N super(11)(1-carboxypropyl)cyclam)]Cl[middot]H sub(2)O (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 RuNOCl sub(3) 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)Cl sub(2)([kappa] super(3)N super(4),N super(8 ),N super(11)(1-carboxypropyl)cyclam )]Cl[middot]H sub(2)O crystallizes in the triclinic, space group P1 No. 2, with unit cell parameters of a = 8.501(1) [Angstrom], b = 9.157(1) [Angstrom], c = 14.200(1) [Angstrom], [alpha] = 72.564(5)[degrees], [beta] = 82.512(5)[degrees], [gamma] = 80.308(5)[degrees], and Z = 2. The Ru-N interatomic distance and bond angle in the [Ru-NO] unit are 1.739(2) [Angstrom] and 167.7(2)[degrees], respectively. ESI-MS/MS shows characteristic dissociation chemistry that initiates by HCl or NO loss. The IR spectrum displays a v(NO) at 1881 cm super(-1) indicating a nitrosonium character. The electronic spectrum shows absorptions bands at 264 nm (log [varepsilon] = 3.27), 404 nm (log [varepsilon] = 2.53), and 532 nm (log [varepsilon] = 1.88). super(1)H and super(13)C 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 [kappa] super(3) instead of the expected [kappa] super(4) denticity.
ISSN:0020-1669
DOI:10.1021/ic702078p