Thiolato-technetium complexes. 4(1): Synthesis,characterization and electrochemical properties of bis(1,2-bis(dimethylphosphino)-ethane)technetium(III) complexes with arene-thiolato ligands |
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| Authors: | Takumi Konno Renato Seeber Jon R. Kirchhoff William R. Heineman Edward Deutsch Mary Jane Heeg |
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| Affiliation: | (1) Biomedical Chemistry Research Center, Department of Chemistry, University of Cincinnati, 45221-0172 Cincinnati, Ohio, USA;(2) Present address: Department of Chemistry, University of Toledo, 43606 Toledo, OH, USA;(3) Present address: Mallunkrodt Medical Inc., 675 McDonnell Blvd, 63134 St Louis, MO, USA;(4) Department of Chemistry, Wayne State University, 48202-3929 Detroit, Michigan, USA |
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| Abstract: | ![]()
Summary The reaction of trans-[Tcv(OH)(O)(DMPE)2]2+ (DMPE = 1,2-bis(dimethylphosphino)ethane) with a series of arenethiols in base produces the novel complexes cis-[TcIII-(SC6H4X-p)2 (DMPE)2]+ for X = H, Cl, Me, OMe, t-Bu. One of the complexes has been characterized by X-ray crystallography: cis-[Tc(SPh)2(DMPE)2]PF6, chemical formula Tc1S2P5F6C24H42, crystallizes in the orthorhombic space group P21nb with Z = 4 and lattice parameters a = 9.311(1) Å, b=11.190(2) Å, c = 31.936(4) Å, Vol = 3327.3(8) Å3. The final weighted R-value was 0.033. Averaged structural parameters are Tc—S = 2.29(2) Å, Tc—P (trans to P) = 2.42(1) Å, Tc—P (trans to S) = 2.49(3) Å, Tc—S—C = 118.5(5)°. The complexes have been characterized by FAB mass spectrometry and u.v.-vis. spectroscopy. The visible region charge transfer bands are diagnostic for cis geometry in the [Tc(SR)2(DMPE)2]+ complexes. Electrochemical and spectroelectrochemical measurements show reversible TcIII/II redox couples in the range -0.19V to -0.38V versus Ag/AgCl (3 M NaCl). Irreversible couples are exhibited at ca. -1.1 V to -1.2 V for TcII/I and +0.7V to +0.9V for TcIV/III. Variation in redox potential is discussed in terms of sulphur nucleophilicity.On leave from the Department of Chemistry, The University of Tsukuba, Tsukuba, Ibaraki 305, Japan.On leave from Dipartimento di Chimica dell'Universita' di Sassari, Via Vienna, 2-Sassari, Italy. |
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