Electrochemistry and spectroelectrochemistry of [Re(1,2-bis(dimethylphosphino)ethane)3]+

Absorbance‐Based Spectroelectrochemical Sensor for [Re(dmpe)3]+ (dmpe=dimethylphosphinoethane)

“…The reversibility of the Re I/II couple is affected by the potential window used for cyclic voltammetry. As previously reported for nonaqueous solutions, the cathodic peak of the reversible Re I/II couple is decreased after scanning past 950 mV, where Re II is oxidized to Re III which decomposes due to loss of a dmpe ligand [7]. As shown in Figure 4, when a 0.05 mM [Re(dmpe) 3 ] þ solution was allowed to equilibrate with the SSEBS film, then scanned from À 600 mV to þ 1000 mV, cathodic peak current was reduced relative to the anodic peak.…”

“…This is consistent with reported electrochemical properties for this compound. [5,7,26] The reversible Re I/II couple is centered around 50 mV, but further oxidation to Re III at 950 mV decreases the peak current for reduction of Re II back to Re I . Scanning for a second cycle shifted the oxidation peak at 950 mV to 980 mV and the reversible oxidation/reduction peaks for Re I/II were almost completely gone.…”

Three-component spectroelectrochemical sensor module for the detection of pertechnetate (TcO4-)

“…In aqueous solution, [Re(dmpe) 3 ] + absorbs at 250 nm ( ε = 21700 m -1 cm -1 ) but has no absorption in the visible region; [Re(dmpe) 3 ] 2 + also absorbs at 250 nm ( ε = 7740 m -1 cm -1 ) and has visible absorption at 530 nm ( ε = 2110 m -1 cm -1 ) Brought to you by | Carleton University OCUL Authenticated Download Date | 6/13/15 9:29 PM well-defined, electrochemically reversible redox couple for the [Re(dmpe) 3 ] + /2 + at E ° ′ = 50 mV (vs. Ag/AgCl in water) as shown in Eq. (4) below: ( Libson et al 1988, Roodt et al 1991, Deng et al 1997, Kirchhoff et al 1997 ( Morris et al 2009 ). The sensor consisted of an optically transparent ITO electrode coated with a thin film of various polymers that contacted the sample solution and that were chosen to preconcentrate the analyte.…”

Non-Pertechnetate Technetium Sensor Research and Development

“…99 Tc, a nuclear fission byproduct, has a very long half-life, no known non-radioactive isotopes, and has the potential to migrate in ground water with little retardation (Schulte and Scoppa 1987;Schwochau 2000). Natural abundance rhenium (Re) has been used as a surrogate for technetium (Tc), which is often used in medical applications as an imaging agent (Deng et al 1997;Deutsch et al 1986;Verbruggen 2005), and therefore has well-known electrochemical and optical properties (Deng et al 1997;Kirchhoff et al 1997;Kirchhoff et al 1988;Lisbon et al 1988;Roodt et al 1991;Woolf 1961). Since analogous Re and Tc compounds generally have nearly identical chemical properties, we are initially targeting our studies using [Re(CO) 3 (H 2 O) 3 ] + , and will progress to using [Tc(CO) 3 (H 2 O) 3 ] + after the prototype sensor is tested.…”