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Technetium electrochemistry. 7. Electrochemical and spectroelectrochemical studies on technetium(III) and -(II) complexes containing polypyridyl ligands

Journal Article · · Inorganic Chemistry; (United States)
DOI:https://doi.org/10.1021/ic00004a018· OSTI ID:6065307
;  [1]
  1. Univ. of Cincinnati, OH (United States)
+ Show Author Affiliations
The redox properties of a series of technetium(III/II) complexes of the general formula cis(X), trans(P)-(Tc{sup III/II}X{sub 2}(PR{sub w}R{prime}){sub 2}L){sup 10+}, where X = Cl or Br, PR{sub 2}R{prime} = dimethylphenylphosphine or ethyldiphenylphosphine, and L = 2,2{prime}-bipyridine (bpy), 4,4{prime}-dimethyl-2,2{prime}-bipyridine (Me{sub 2}bpy), or 1,10-phenanthroline (phen), were investigated in 0.1 M TEAP/acetonitrile by cyclic voltammetry at a platinum-disk electrode. These complexes exhibit diffusion-controlled, 1-equiv Tc(IV)/Tc(III) redox couples and also Tc(III)/Tc(II) redox couples. Spectropotentiostatic experiments on three complexes of this class in 0.5 M TEAP/DMF confirm the 1-equiv character of the Tc(III)/Tc(II) couple. The electrochemical behavior of Tc(II) complexes of the general formula trans(P)-(TcX(PR{sub 2}R{prime}){sub 2}terpy){sup +}, terpy = 2,2{prime}:6{prime},2{double prime}-terpyridine, was also investigated under the same conditions as above. These complexes exhibit diffusion-controlled, 1-equiv Tc(III)/Tc(II) redox couples and Tc(II)/Tc(I) redox couples. Spectropotentiostatic experiments on trans(P)-(TcCl(PMe{sub 2}Ph){sub 2}terpy){sup +} confirm the 1-equiv character of the Tc(III)/Tc(II) couple but show that the Tc(II)/Tc(I) couple is not reversible on the spectropotentiostatic time scale.
OSTI ID:
6065307
Journal Information:
Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:4; ISSN 0020-1669; ISSN INOCA
Country of Publication:
United States
Language:
English

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AROMATICS
AZAARENES
AZINES
BIPYRIDINES
BROMINE COMPOUNDS
CHEMICAL REACTIONS
CHLORINE COMPOUNDS
COMPLEXES
DATA
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHENANTHROLINES
PHOSPHINES
PHOSPHORUS COMPOUNDS
PYRIDINES
REDOX REACTIONS
TECHNETIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY