Ru(II) and Ru(III) complexes with cyclam and related species

Tfouni, Elia; Ferreira, Kleber Queiroz; Doro, Fábio Gorzoni; Silva, Roberto Santana da; Rocha, Zildete

doi:10.1016/j.ccr.2004.09.009

Cited by 84 publications

(170 citation statements)

References 117 publications

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“…This decrease undoubtedly suggests the photochemical labilization of NO (equation 10). Similar changes in the infrared spectrum had already been observed with 10 -2 mol L -1 trans- [RuCl(NO) 14,17,18,46,67 The quantum yields decrease as pH decreases and as the irradiation wavelength increases, being noticeable only at l irr < 370 nm. The larger quantum yields achieved at larger pH values can be explained, as in the case of the analogous trans-[Ru(NO)(NH 3 ) 4 (py-X)] 3+ complexes, 46 as follows.…”

supporting

confidence: 75%

“…This feature has been assigned to solid state effects. 18 However, only one peak at 1875 cm -1 appears in the spectrum of the aqueous solution of trans-[Ru(NO)Cl(1-pramcyH)] (PF 6 ) 3 ; it is shifted to 1864 cm −1 in acetonitrile (Figure 2), indicating a solvent dependence for the n(NO). These peaks support the nitrosonium character of NO in this complex.…”

mentioning

confidence: 99%

“…[14][15][16][17][18]34,[40][41][42][43][44][45][46][47][48][49] These properties can be tuned by the adequate choice of ligands. 14,18 It should be pointed out that interesting biological activities for several of these complexes have already been reported. 14,17,21,33,34,[37][38][39] Because NO can be either beneficial or harmful depending on its bioavailability, compounds capable of releasing NO in a specific biological target have potential biological applications and could be useful tools to study the physiological action of NO.…”

mentioning

confidence: 99%

“…Efforts from this laboratory have been directed toward this goal, using several strategies. One of such approaches involves the functionalization of ruthenium nitrosyl complexes, so they can be linked to important entities such as antibodies and to surfaces, in order to obtain selective NO donor drugs or devices.We 18 One of their fundamental properties is the size of the macrocyclic ring. A change in ring size has been shown to markedly affect the electronic spectra, redox potentials, and reactivities of the complexes.…”

mentioning

confidence: 99%

“…A change in ring size has been shown to markedly affect the electronic spectra, redox potentials, and reactivities of the complexes. 18 Substitution in the ligand may also affect some properties, such as reactivity.We have reported the syntheses and reactivity 18 However, in very few cases, the substitution in the cyclam ligand imparts a drastic shift from the expected properties of the metal complex. 19,50,51 These complexes present interesting configurations by exhibiting a κ 3 denticity for the mono-N-substituted 1-(carboxypropyl)cyclam ligand in fac- [Ru(NO) …”

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confidence: 99%

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Chemical and photochemical properties of a ruthenium nitrosyl complex with the N-monosubstituted cyclam 1-(3-Propylammonium)-1,4,8,11-tetraazacyclotetradecane

Ferreira¹,

Tfouni²

2010

J. Braz. Chem. Soc.

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O complexo aminofuncionalizado trans-[Ru(NO)Cl(1-pramcyH)](PF 6 ) 3 (1-pramcyH = 1-(3-propilamônio)-1,4,8,11-tetraazaciclotetradecano) foi sintetizado através da reação do trans-[RuCl(tfms)(1-pramcyH)](tfms) 2 (tfms = trifluorometanossulfonato) com óxido nítrico (NO) em solução aquosa ácida. O complexo foi caracterizado por análise elementar, espectroscópica (UVvis, IV, RMN de 1 H e 13 C) e eletroquímica. Dois valores de pK a (7,0 e 8,2) foram determinados para trans- [Ru(NO) ](PF 6 ) 3 e foram atribuídos a um dos prótons do grupo amina do cyclam e ao propilamônio. A redução do trans- [Ru(NO) ] 3+ leva à saída rápida de cloreto seguida de saída lenta de NO, enquanto a irradiação do complexo em solução aquosa desaerada resulta na labilização fotoquímica do NO. O rendimento quântico para a fotoaquação do NO diminui com o aumento do comprimento de onda de irradiação e com a diminuição do pH, e é observável apenas a l irr < 370 nm. O comportamento do trans- [Ru(NO) ] 3+ é semelhante ao do complexo análogo trans- [Ru(NO) Cl(cyclam)] 2+ , porém difere daquele do complexo com carboxipropil como substituinte.The amine-functionalized trans- [Ru(NO) ](PF 6 ) 3 complex (1-pramcyH = 1-(3-propylammonium)-1,4,8,11-tetraazacyclotetradecane) was synthesized from trans- [RuCl(tfms) (1-pramcyH)](tfms) 2 (tfms = trifluoromethanesulfonate) in acidic aqueous solution in the presence of nitric oxide (NO). The complex was characterized by elemental, spectroscopic (UV-Vis, IR, 1 H and 13 C NMR) and electrochemical analyses. Two pK a values (7.0 and 8.2) were estimated for trans- [Ru(NO) ](PF 6 ) 3 and were assigned to one of the cyclam nitrogen protons and to the protonated aminopropyl group. Reduction of trans- [Ru(NO) ] 3+ results in rapid loss of chloride followed by slower loss of NO, while irradiation of the complex in aqueous deaerated conditions suggests photochemical labilization of NO. The quantum yields for NO photoaquation decrease as the irradiation wavelength increases, being noticeable only at l irr < 370 nm, and increase as pH increases. The behavior of trans- [Ru(NO) ] 3+ , which contains an aminopropyl substituted cyclam, parallels that reported for the analogous complex with the unsubstituted ligand, but differs from that described for the complex in which carboxypropyl is the substituent. Keywords: nitrosyl, ruthenium, nitric oxide donor, substituted cylam, mono-N-functionalized cyclam IntroductionThe discovery of the participation of nitric oxide (NO) in a wide range of physiological processes and pathologies 1 has launched investigations on NO donors, including metal nitrosyl complexes in solution or immobilized in matrices, aiming at the understanding of both fundamental aspects and biological activity for potential applications. Among the NO donors, ruthenium nitrosyl complexes are particularly attractive because they are stable, can be either water soluble or not, deliver NO at different rates upon activation by reduction at biologically accessible Chemical and Photochemical Properties of a Ruthenium Nitrosyl...

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supporting

confidence: 75%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Chemical and photochemical properties of a ruthenium nitrosyl complex with the N-monosubstituted cyclam 1-(3-Propylammonium)-1,4,8,11-tetraazacyclotetradecane

Ferreira¹,

Tfouni²

2010

J. Braz. Chem. Soc.

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Two heptadentate Co(III) and Mn(III) complexes with partially deprotonated cyclen derivative bearing four hydroxypropyl pendants: structure, DNA binding and DNA cleavage

Yin

Wen

Geng

et al. 2012

Applied Organom Chemis

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4,7,10-tetra-(2-hydroxypropyl)-l,4,7,10-tetraazacyclododecane] using electrospray ionization mass spectrometry and X-ray photoelectron spectrometery. The characterizations confirmed that the valences of the metal ions increased from divalent to trivalent due to deprotonation of one OH group (H 4 L was in the form of H 3 L À ). Owing to the instability of Co(III) and Mn(III) in both air and in solution, they preferred to exist in divalent form. The two heptadentate complexes are extraordinary in that the chiral pendants of the complexes are different in configuration. Spectroscopic studies, viscosity measurements, thermal denaturation experiments and circular dichroism spectra demonstrated that the complexes were prone to interact with DNA by groove binding. At micromolar concentrations and under physiological conditions, the two complexes were able to oxidatively cleave the supercoiled pUC19 plasmid DNA into its nicked and linear forms. Mechanistic studies using various additives suggest the complexes had structures different from those of other inorganic complexes. These are the first reported inorganic complexes not containing planar aromatic ligands and yet binding at the major groove.

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Design of phenanthrimidazole‐pendant cyclam and cyclen macrocyclic complex ligands as inorganic hosts: Photophysics, electrochemistry, and bimetallic complex formation

Obalı

2019

Journal of Heterocyclic Chem

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Novel ruthenium(II)bpy complexes of the phenanthrimidazole-pendant cyclen and cyclam macrocyclic ligands were synthesized as inorganic host molecules.Inorganic host design was planned as a "complex ligand" form because of its tetraaza macrocyclic unit, which has the ability to coordinate to the metals.Photophysical properties and metal selectivity of inorganic hosts RuL1A and RuL2 complex ligands were investigated by UV-vis and fluorescence spectros-

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Ru(II) and Ru(III) complexes with cyclam and related species

Cited by 84 publications

References 117 publications

Chemical and photochemical properties of a ruthenium nitrosyl complex with the N-monosubstituted cyclam 1-(3-Propylammonium)-1,4,8,11-tetraazacyclotetradecane

Chemical and photochemical properties of a ruthenium nitrosyl complex with the N-monosubstituted cyclam 1-(3-Propylammonium)-1,4,8,11-tetraazacyclotetradecane

Two heptadentate Co(III) and Mn(III) complexes with partially deprotonated cyclen derivative bearing four hydroxypropyl pendants: structure, DNA binding and DNA cleavage

Design of phenanthrimidazole‐pendant cyclam and cyclen macrocyclic complex ligands as inorganic hosts: Photophysics, electrochemistry, and bimetallic complex formation

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