Technetium electrochemistry. 1. Spectroelectrochemical studies of halogen, diars, and diphos complexes of technetium in nonaqueous media

Hurst, Roger W.; Heineman, William R.; Deutsch, Edward

doi:10.1021/ic50224a031

Cited by 40 publications

(7 citation statements)

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“…Despite mixed electrochemical and chemical pathways of pertechnetate ions reduction, the technetium compounds are good subjects for spectroelectrochemical studies [ 9 , 10 ]. However, only in a few cases the spectroelectrochemical studies were performed in aqueous solutions [ 11 – 13 ].…”

Section: Introductionmentioning

confidence: 99%

“…The spectroelectrochemistry is particularly useful [ 9 ] for determining the mechanism of electrochemical reduction processes of technetium(VII). The working electrode is usually manufactured from an optically transparent material [ 10 , 15 ], e.g. from RVC (Reticulated Vitreous Carbon), which was applied by Norwell and Mamantov [ 16 ] and Marassi et al [ 17 – 19 ] in an optically transparent thin layer cell (OTTL-RVC cell).…”

Section: Introductionmentioning

confidence: 99%

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Thin layer spectroelectrochemical (RVC-OTTLE) studies of pertechnetate reduction in acidic media

Chotkowski

Czerwiński

2014

J Radioanal Nucl Chem

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The electroreduction of the pertechnetate ions has been examined in sulfuric acid solutions (0.5–4 M) using optically transparent thin layer spectroelectrochemical (RVC-OTTLE) cell. Soluble Tc(III), TcO2+ and [Tc(μ-O)2Tc]3+/4+ species with absorption bands at 420–450, 400, and 502 nm, respectively, were found to be formed during the reduction of TcO4− ions. The strongly acidic medium was found to stabilize technetium ionic forms with lower oxidation states. Spectroelectrochemical measurements performed in 4 M H2SO4 show different stability of dimeric structure of Tc(III, IV) and simple TcO2+ ions. The monooxotechnetium(IV) ions can be electrooxidized at potentials lower than 0.6 V versus Ag,AgCl(sat.) while dimeric structures of Tc, [Tc(μ-O)2Tc]3+/4+, are electrooxidized to pertechnetate ions at potentials higher than 0.8 V versus Ag,AgCl(sat.)

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Thin layer spectroelectrochemical (RVC-OTTLE) studies of pertechnetate reduction in acidic media

Chotkowski

Czerwiński

2014

J Radioanal Nucl Chem

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“…[T~(diars)~Cl,]' and [Tc(dipho~)~Br,]+ have been prepared and shown by single-crystal X-ray diffraction to have trans configurations. 268 The Tc"'/Tc" reduction potential of several such compounds is shown to increase in the order C1 < Br < I and diars < diphos. [Tc(diphos),H,Cl] has also been prepared.269…”

Section: Manganese Technetium and Rheniummentioning

confidence: 99%

Chapter 7. Ti, Zr, Hf; V, Nb, Ta; Cr, Mo, W; Mn, Tc, Re

Newbery¹

1981

Annu. Rep. Prog. Chem., Sect. A

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GeneralThis Section contains reference to general topics and to reviews of the chemistry of the early transition elements.Transition-metal-nitrogen multiple bonds form the topic of an interesting compilation' that stresses the variety of structural types possible in this area. Many vibrational spectroscopic data are included together with relevant structural data. The transition-metal co-ordination chemistry of the uncharged thio-, seleno-, and telluro-ethers is the subject of a 40-page review.2 Complexes are systematically classified by group and available structural data of these complexes are used to discuss the likely bonding modes. Thio-species of a different type (MS4'"-, thiometalate anions) are discussed in an extensive account3 that stresses their wide range of interesting chemistry. Most of the species involve an early transition metal (e.g. V or Mo), and apart from a discussion of bonding schemes there is a useful didactic account of the application of spectroscopic methods.The final section deals with the formation of heterometallic species (i.e. MS4"considered as a ligand) and includes data of relevance to the bioinorganic topics of nitrogenase and Cu-Mo antagonism in ruminants.An extensive (500 references) review4 of the co-ordination chemistry of sulphoxide transition-metal complexes includes a considerable amount of comment on the early metals. Structural, spectroscopic, and synthetic aspects of the area are covered.It is not possible to write a sensible review of a 327-page volume dealing with a recent symposium on the reactivity of metal-metal bond^.^ Suffice it to say that the work includes such diverse titles as 'Thermochemistry of metal-metal bonds'and 'Anything one can do, 2 can do tooand it's more interesting'. It is thus an essential addition to the literature of a current rapidly developing field.

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“…Diars complexes have attracted interest in the field of radiopharmaceuticals due to the selective uptake of [Tc(diars) 2 Cl 2 ]Cl in the brain tissue of test animals [2,3]. Cationic technitium ( 99 Tc) complexes that incorporate tertiary arsine ligands are developed as potential myocardial imaging agents [4,5] and are especially benefited from application of electrochemical and spectroelectro chemical techniques [6]. The analogous complexes of the radioactive isotope of Rhenium, 186 Re have been investigated with regard to their potential use in nuclear medicine [7,8].…”

Section: Introductionmentioning

confidence: 99%

Electrochemical studies on [M(diars)2X2]+ where [X = Cl, Br; M = Os, Re, Ru, Rh; diars = o-phenylenebis (dimethylarsine)] at bare and Nafion modified electrodes

Suganthi¹,

Rajarajan²,

Murugesan

2008

J Appl Electrochem

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Electrochemical studies on [M(diars) 2 X 2 ] + where [X = Cl, Br; M = Os, Re, Ru, Rh; diars = o-phenylenebis (dimethylarsine)] at bare and Nafion modified electrodesAbstract The voltammetric behaviour of the M(III/II) redox couple of the complexes of the general formula [M(diars) 2 X 2 ] + where M = Os, Re, Ru, Rh and diars = o-phenylenebis-(dimethylarsine) has been investigated in aqueous and aqueous/ethanol solvents at bare and Nafion modified electrodes. The formal reduction potential falls within the range of 0.097-0.0920 V and increases with the dielectric constant of the solvent. In acertonitrile, both the oxidized and reduced forms of the complex showed no adsorption at the surface of the glassy carbon electrode as shown by cyclic voltammetry. The electrochemistry is consistent with a quasireversible one electron transfer between the di and tri cationic forms of the complexes. A current-enhancement of *2 was observed at Nafionmodified glassy carbon over the bare electrode. Well defined voltammograms were obtained at Nafion-modified glassy carbon with a detectable signal down to 10 -9 M range by differential pulse voltammetry. Electrochemical detection of dopamine in presence of [Os(4-mediars) 2 Cl 2 ] + at Nafion modified electrode indicates an increase in peak current. This shows that this complex acts as biochemicalsensor for dopamine.

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Technetium electrochemistry. 1. Spectroelectrochemical studies of halogen, diars, and diphos complexes of technetium in nonaqueous media

Cited by 40 publications

References 5 publications

Thin layer spectroelectrochemical (RVC-OTTLE) studies of pertechnetate reduction in acidic media

Thin layer spectroelectrochemical (RVC-OTTLE) studies of pertechnetate reduction in acidic media

Chapter 7. Ti, Zr, Hf; V, Nb, Ta; Cr, Mo, W; Mn, Tc, Re

Electrochemical studies on [M(diars)2X2]+ where [X = Cl, Br; M = Os, Re, Ru, Rh; diars = o-phenylenebis (dimethylarsine)] at bare and Nafion modified electrodes

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