Electrochemical and chemical properties of dithiocarbamato complexes of ruthenium(II), ruthenium(III), and ruthenium(IV)

Wheeler, S. H.; Mattson, Bruce; Miessler, G. L.

doi:10.1021/ic50180a034

“…This reaction at the electrode surface agrees with the oxidation of other Ru(III)dithiocarbamates as observed by Wheeler [27]. The scanning of the electrode between the potentials 0.0 V and þ0.8 V for 50 cycles did not show any appreciable decrease in current.…”

Section: Oxidation Studiessupporting

confidence: 90%

Electrocatalytic Oxidation of Sulfhydryl Compounds at Ruthenium(III) Diphenyldithiocarbamate Modified Carbon Paste Electrode

Nalini

¹

,

Narayanan

²

1998

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An aqueous insoluble new redox mediator ruthenium(III)-diphenyldithiocarbamate has been used as a modifier to prepare a carbon paste electrode. The modified electrode was characterized by cyclic voltammetry by varying the pH of the medium and also the scan rate. The electrode was scanned between 0.0 V and þ0.8 V in 0.1 M KNO 3 medium. Anodic and cathodic peaks were observed at þ0.38 V and þ0.22 V, respectively, for a scan rate of 100 mV/s. The modified electrode is found to oxidize electrocatalytically cysteine and glutathione. Conditions such as pH and scan rate have been optimized for the determination of both compounds. Linear response for cysteine is in the range of 0.00-15.20 mg/L, with a correlation coefficient (r), of 0.9992. Standard deviation for 10 repetitive determinations was found to be 0.0756. The linear range for glutathione is 0.00-30.40 mg/L, with a value of 0.9995 for r, and the standard deviation is 0.1449. The stability and reproducibility of the electrode for the determination of cysteine and glutathione were also discussed. Hydrodynamic voltammogram was also recorded for the electrocatalytic oxidation of the sulfhydryl compounds. Amperometric determination and studies on the stability of the electrode for a period of 10 days were also carried out.

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“…The tris(dithiocarbamate) complexes all have a low-spin d 5 electronic configuration and are easily converted into [Ru 2 (S 2 CNR 2 ) 5 ] + upon addition of Lewis acids [104]. Isomers of the latter are known containing two ( -isomers) or three ( -isomers) bridging dithiocarbamate ligands [104,105]. Seven coordinate ruthenium(IV) complexes [RuCl(S 2 CNR 2 ) 3 ] are also known but when dissolved in coordinating solvents such as acetonitrile the halide is displace to give ionic complexes [Ru(MeCN)(S 2 CNR 2 ) 3 ]Cl [105].…”

Section: Iron and Ruthenium Chemistrymentioning

confidence: 99%

“…Isomers of the latter are known containing two ( -isomers) or three ( -isomers) bridging dithiocarbamate ligands [104,105]. Seven coordinate ruthenium(IV) complexes [RuCl(S 2 CNR 2 ) 3 ] are also known but when dissolved in coordinating solvents such as acetonitrile the halide is displace to give ionic complexes [Ru(MeCN)(S 2 CNR 2 ) 3 ]Cl [105]. Extensive electrochemical studies have been carried out on tris(dithiocarbamate) complexes [Ru(S 2 CNR 2 ) 3 ] [102,105].…”

Section: Iron and Ruthenium Chemistrymentioning

confidence: 99%

“…Seven coordinate ruthenium(IV) complexes [RuCl(S 2 CNR 2 ) 3 ] are also known but when dissolved in coordinating solvents such as acetonitrile the halide is displace to give ionic complexes [Ru(MeCN)(S 2 CNR 2 ) 3 ]Cl [105]. Extensive electrochemical studies have been carried out on tris(dithiocarbamate) complexes [Ru(S 2 CNR 2 ) 3 ] [102,105]. The oxidation chemistry is highly dependent upon the nature of the solvent and in acetonitrile the one-electron oxidation product is [Ru(MeCN)(S 2 CNR 2 ) 3 ] + [105].…”

Section: Iron and Ruthenium Chemistrymentioning

confidence: 99%

“…Extensive electrochemical studies have been carried out on tris(dithiocarbamate) complexes [Ru(S 2 CNR 2 ) 3 ] [102,105]. The oxidation chemistry is highly dependent upon the nature of the solvent and in acetonitrile the one-electron oxidation product is [Ru(MeCN)(S 2 CNR 2 ) 3 ] + [105]. In dichloromethane two oneelectron oxidations are observed, the first of which is irreversible while the second has some reversibility [102].…”

Section: Iron and Ruthenium Chemistrymentioning

confidence: 99%

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Metal-dithiocarbamate complexes: chemistry and biological activity

Hogarth¹

2012

MRMC

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Dithiocarbamates are highly versatile mono-anionic chelating ligands which form stable complexes with all the transition elements and also the majority of main group, lanthanide and actinide elements. They are easily prepared from primary or secondary amines and depending upon the nature of the cation can show good solubility in water or organic solvents. They are related to the thiuram disulfides by a one-electron redox process (followed by dimerisation via sulfur-sulfur bond formation) which is easily carried out upon addition of iodide or ferric salts. Dithiocarbamates are lipophilic and generally bind to metals in a symmetrical chelate fashion but examples of other coordination modes are known, the monodentate and anisobidentate modes being most prevalent. They are planar sterically non-demanding ligands which can be electronically tuned by judicious choice of substituents. They stabilize metals in a wide range of oxidation states, this being attributed to the existence of soft dithiocarbamate and hard thioureide resonance forms, the latter formally resulting from delocalization of the nitrogen lone pair onto the sulfurs, and consequently their complexes tend to have a rich electrochemistry. Tetraethyl thiuramdisulfide (disulfiram or antabuse) has been used as a drug since the 1950s but it is only recently that dithiocarbamate complexes have been explored within the medicinal domain. Over the past two decades anti-cancer activity has been noted for gold and copper complexes, technetium and copper complexes have been used in PET-imaging, dithiocarbamates have been used to treat acute cadmium poisoning and copper complexes also have been investigated as SOD inhibitors.

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Electrocatalytic Oxidation of Sulfhydryl Compounds at Ruthenium(III) Diphenyldithiocarbamate Modified Carbon Paste Electrode

Nalini¹,

Narayanan²

1998

View full text Add to dashboard Cite

An aqueous insoluble new redox mediator ruthenium(III)-diphenyldithiocarbamate has been used as a modifier to prepare a carbon paste electrode. The modified electrode was characterized by cyclic voltammetry by varying the pH of the medium and also the scan rate. The electrode was scanned between 0.0 V and þ0.8 V in 0.1 M KNO 3 medium. Anodic and cathodic peaks were observed at þ0.38 V and þ0.22 V, respectively, for a scan rate of 100 mV/s. The modified electrode is found to oxidize electrocatalytically cysteine and glutathione. Conditions such as pH and scan rate have been optimized for the determination of both compounds. Linear response for cysteine is in the range of 0.00-15.20 mg/L, with a correlation coefficient (r), of 0.9992. Standard deviation for 10 repetitive determinations was found to be 0.0756. The linear range for glutathione is 0.00-30.40 mg/L, with a value of 0.9995 for r, and the standard deviation is 0.1449. The stability and reproducibility of the electrode for the determination of cysteine and glutathione were also discussed. Hydrodynamic voltammogram was also recorded for the electrocatalytic oxidation of the sulfhydryl compounds. Amperometric determination and studies on the stability of the electrode for a period of 10 days were also carried out.

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Electrochemical and chemical properties of dithiocarbamato complexes of ruthenium(II), ruthenium(III), and ruthenium(IV)

Cited by 42 publications

References 27 publications

Electrocatalytic Oxidation of Sulfhydryl Compounds at Ruthenium(III) Diphenyldithiocarbamate Modified Carbon Paste Electrode

Electrocatalytic Oxidation of Sulfhydryl Compounds at Ruthenium(III) Diphenyldithiocarbamate Modified Carbon Paste Electrode

Metal-dithiocarbamate complexes: chemistry and biological activity

Electrocatalytic Oxidation of Sulfhydryl Compounds at Ruthenium(III) Diphenyldithiocarbamate Modified Carbon Paste Electrode

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