Synthesis and Reactivity of Ru-, Os-, Rh-, and Ir-Halide−Sulfoxide Complexes

Alessio, Enzo

doi:10.1021/cr0307291

Cited by 204 publications

(157 citation statements)

References 414 publications

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“…[8,[10][11][12][13][14] In addition, several ligands with N-and O-donor atoms were studied in substitution reactions of both isomers of [RuCl2(dmso)4]. [15] This was -in part-motivated by the expected biological effects of the products. [16][17][18][19] While 1 itself also shows antitumor and remarkable antimetastatic activity, certain of its substituted derivatives are even more effective.…”

Section: Introductionmentioning

confidence: 99%

The dual role of cis-[RuCl2(dmso)4] in the synthesis of new water-soluble Ru(II)–phosphane complexes and in the catalysis of redox isomerization of allylic alcohols in aqueous–organic biphasic systems

Udvardy

Bényei

Kathó

2012

Journal of Organometallic Chemistry

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New air-stable, water-soluble Ru(II)-phosphane complexes were synthesized in high purity by the reaction of cis-[RuCl2(dmso)4] with 2 equivalents of 1,3,5-triaza-7-phosphaadamantane (pta) and its N-methyl and N-benzyl derivatives (pta-Me and pta-Bn, respectively). All new complexes were characterized by elementary analysis and spectroscopic methods (NMR, ESI  1 and the new complexes actively catalyzed the isomerization of allylic alcohols. MS) and the molecular structures of cis-cis-trans-[RuCl2(dmso)2(pta)2], cis-cis-trans-

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Section: Introductionmentioning

confidence: 99%

The dual role of cis-[RuCl2(dmso)4] in the synthesis of new water-soluble Ru(II)–phosphane complexes and in the catalysis of redox isomerization of allylic alcohols in aqueous–organic biphasic systems

Udvardy

Bényei

Kathó

2012

Journal of Organometallic Chemistry

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“…This new feature is ascribed to the O-bonded isomer. [15,16] The presence of a photostationary state with white light irradiation indicates an excited-state photochemical pathway for O!S isomerization from longer wavelengths. Accordingly, 470 nm irradiation of a solution that contains predominately the O-isomer resulted in a decrease of the absorbance at 472 nm concomitant with an increase at 370 nm (F O!S = Figure 1.…”

mentioning

confidence: 99%

Two‐Color Reversible Switching in a Photochromic Ruthenium Sulfoxide Complex

McClure

Rack

2009

Angew Chem Int Ed

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Reversible, external triggering of molecules between two ground states is central to the operation of modern molecular machines. [1][2][3] A desirable trigger is light, as it provides an ample amount of energy in a short burst of time. Although light is commonly employed for the formation of many different types of metastable states, [4][5][6][7][8] in practice it is difficult to employ light to regenerate the initial ground state. The enthalpic and entropic factors that favor the photochemical generation of the metastable state from the ground state must necessarily be disfavored for the opposing photochemical reaction. Moreover, the photoproduct often reverts to the ground state thermally. Irradiation of photochromic compounds yields metastable states that exhibit distinct electronic structures compared to their ground states.[9] Whilst a number of organic photochromic compounds feature reversible or two-color photoswitching between metastable and ground states, such reactivity is rare in transition metal complexes.[10]Herein, we report our findings on a ruthenium sulfoxide complex that features two-color photochromism.The complex [Ru(bpy) 2 (pySO)](PF 6 ) 2 (bpy = 2,2'-bipyridine, pySO = 2-(isopropylsulfinylmethyl)pyridine) was prepared from reaction of cis-[Ru(bpy) 2 Cl 2 ] with pySO. The structure and formulation of the complex was verified by oneand-two-dimensional 1 H NMR, IR spectroscopy, and elemental analysis. The 1 H NMR spectrum is consistent with the presence of two isomers, which are most likely diastereomers, as both the ruthenium and sulfur centers are chiral. Elemental analysis of the isomeric mixture supports this assignment. The lowest-energy transition in the electronic spectrum occurs at 370 nm (e = 7250 cm À1 m À1 ) and is assigned to a Ru dp!bpy p* charge-transfer transition based on its energy and intensity (Figure 1). This transition is similar to that observed for other chelating S-bonded sulfoxides.[11] Furthermore, the structurally characterized complex [Ru(bpy) 2 (py)(dmso)] 2+ (dmso = dimethylsulfoxide), which has no chelation, features a maximum absorbance at 400 nm for the S-bonded isomer.[12]Therefore, the chelate complex exhibits an additional 2000 cm À1 of stabilization relative to the non-chelate form. White light irradiation of [Ru(bpy) 2 (pySO)]2+ in propylene carbonate solution results in a decrease in the absorbance at 370 nm concomitant with an increase at 472 nm (Figure 1, inset). In accord with other ruthenium sulfoxide complexes, [13] the spectral changes indicate an intramolecular S!O isomerization, with an isosbestic point at 408 nm. However, the observed spectral changes are muted in comparison to these other complexes. We questioned whether or not this spectrum represented a photostationary state. Accordingly, irradiation of this solution with 355 nm light resulted in a more pronounced absorbance at 472 nm (quantum efficiency F S!O = 0.11(2)). This value is similar to that of the Obonded isomer of [Ru(bpy) 2 (py)(dmso)] 2+ (476 nm) [12] and [Ru(bpy) 2 (pic)] + (483...

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“…LDH isoenzymes (LDH [1][2][3][4][5] ) were detected by vertical electrophoresis on non-denaturing 7% PAGE using a Tris-glycine buffer, following the methods described [39]. The isoenzymes bands were detected using lithium lactate as a substrate in the presence of cofactors NADH and tetrazolium blue.…”

Section: Determination Of Ldh Activity In Plasmamentioning

confidence: 99%

“…Metal complexes of ruthenium have been for more than twenty years in the focus of many researches in chemistry [1][2][3][4] as well as in medicine [5,6]. Their properties can be altered by the choice of ligands, which means that complexes potentially have multiple applications.…”

Section: Introductionmentioning

confidence: 99%

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In Vivo Enzymes Activities of Some Ru(II) Compounds with N-Alkylphenothiazines

et al. 2016

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The purpose of the present study was to investigate and compare the effects of two ruthenium complexes with trifl uoperazine on acethylcholinesterase enzyme activity and lactate dehydrogenase levels in vivo under physiological conditions in rats blood. Complexes 1 and 2 showed positive effects on acethylcholinesterase at all doses and did not disturb its normal activity. Total LDH activity was inhibited in the presence of both complexes, but Ru(II) complexes showed different effects on the activity of LDH isoenzymes. The activities of LDH 1 and LDH 2 isoenzymes were decreased in all applied doses of the complex 2, while the activity of LDH 2 reduced using complex 1 in the same doses. Results of the present study suggest the neuro-and cardio protective potential of oral administration of complexes 1 and 2, as non-toxic compounds under physiological conditions. These protective effects are the result of their potent antioxidant activity.

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Synthesis and Reactivity of Ru-, Os-, Rh-, and Ir-Halide−Sulfoxide Complexes

Cited by 204 publications

References 414 publications

The dual role of cis-[RuCl2(dmso)4] in the synthesis of new water-soluble Ru(II)–phosphane complexes and in the catalysis of redox isomerization of allylic alcohols in aqueous–organic biphasic systems

The dual role of cis-[RuCl2(dmso)4] in the synthesis of new water-soluble Ru(II)–phosphane complexes and in the catalysis of redox isomerization of allylic alcohols in aqueous–organic biphasic systems

Two‐Color Reversible Switching in a Photochromic Ruthenium Sulfoxide Complex

In Vivo Enzymes Activities of Some Ru(II) Compounds with N-Alkylphenothiazines

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