Technetium electrochemistry. 4. Electrochemical and spectroelectrochemical studies on the bis(tertiary phosphine or arsine (D))rhenium(III) complexes trans-(ReD/sub 2/X/sub 2/)/sup +/ (X = Cl, Br). Comparison with the technetium(III) analogues
The redox properties of a series of rhenium(III) complexes with the general formula trans-(ReD/sub 2/X/sub 2/)/sup +/ (where D is one of the chelating phosphine or arsine ligands 1,2-bis(dimethylphosphino)ethane, 1,2-bis(diethylphosphino)ethane, 1,2-bis(diphenylphosphino)ethane, or 1,2-bis(dimethylarsino)benzene and X is Cl or Br) were investigated in 0.5 M TEAP/DMF by cyclic voltammetry, thin-layer electrochemistry, and thin-layer spectroelectrochemistry. The cationic trans-(ReD/sub 2/X/sub 2/)/sup +/ complexes exhibit a diffusion-controlled, reversible one-electron reduction to the neutral trans-(ReD/sub 2/X/sub 2/)/sup 0/ complexes at a platinum-disk electrode. The formal reduction potential, E/sup 0/', of the Re(III/II) redox couple ranges from -0.205 to 0.450 V vs Ag/AgCl (3 M NaCl). Further reduction to the rhenium(I) anion, trans-(ReD/sub 2/X/sub 2/)/sup -/, is possible; however, the reversibility of this process depends on the nature of the coordinating ligands and the experimental conditions. The Re(II/I) redox couple occurs at an E/sup 0/' value ca. 1.11 V more negative than that of the corresponding Re(III/II) couple. Thin-layer spectroelectrochemistry has been used to study the halogen-to-metal charge-transfer (HTMCT) band(s) of the Re(III) and Re(II) complexes. 36 references, 7 figures, 3 tables.
- Research Organization:
- Univ. of Cincinnati, OH
- DOE Contract Number:
- AC02-80EV10380
- OSTI ID:
- 5796718
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:19; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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62 RADIOLOGY AND NUCLEAR MEDICINE
ARSENIC COMPOUNDS
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
BIOLOGICAL EFFECTS
CHEMISTRY
COMPLEXES
DATA
ELECTROCHEMISTRY
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
HOURS LIVING RADIOISOTOPES
INFORMATION
INTERMEDIATE MASS NUCLEI
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
METASTABLE STATES
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
PHOSPHINES
PHOSPHORUS COMPOUNDS
RADIOISOTOPES
RHENIUM COMPLEXES
SPECTROSCOPY
TECHNETIUM 99
TECHNETIUM COMPLEXES
TECHNETIUM ISOTOPES
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY
YEARS LIVING RADIOISOTOPES