Thiolato-technetium complexes. 5. Synthesis, characterization, and electrochemical properties of bis(o-phenylenebis(dimethylarsine))technetium(II) and -technetium(III) complexes with thiolato ligands. Single-crystal structural analyses of trans-(Tc(SCH sub 3 ) sub 2 (DIARS) sub 2 )PF sub 6 and trans-(Tc(SC sub 6 H sub 5 ) sub 2 (DIARS) sub 2 ) sup 0

Journal Article · Wed Apr 01 00:00:00 EST 1992 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00033a011· OSTI ID:6957500

Konno, Takumi; Heineman, W R; Deutsch, E; Kirchhoff, J R ^[1]; Heeg, M J; Stuckey, J A ^[2]

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1. Univ. of Cincinnati, OH (United States)
2. Wayne State Univ., Detroit, MI (United States)

Three different thiols have been brought into reaction with trans-(Tc(OH)(O)(DIARS){sub 2}){sup 2+} to produce initially the Tc(II) complex, (Tc(SR){sub 2}(DIARS){sub 2}){sup 0}, which can be oxidized to the Tc(III) complex, (Tc(SR){sub 2}(DIARS){sub 2}){sup +} (DIARS = o-phenylenebis(dimethylarsine)). In the case of SR = SCH{sub 3} and SCH{sub 2}C{sub 6}H{sub 5}, the Tc(II) and Tc(III) products were found to be in the trans geometry, while for SR = SC{sub 6}H{sub 5}, both cis and trans isomers were generated. Two of the complexes were structurally characterized by X-ray diffraction. trans-(Tc(SCH{sub 3}){sub 2}(DIARS){sub 2})PF{sub 6}, chemical formula TcAs{sub 4}S{sub 2}PF{sub 6}C{sub 22}H{sub 38}, crystallizes in the monoclinic space group. The Tc atom occupies an inversion center. Representative elemental analyses, FAB mass spectra, and visible-UV spectra are reported. Electrochemical and spectroelectrochemical measurements were taken on trans-(Tc(SCH{sub 3}){sub 2}(DIARS){sub 2}){sup +}, trans-(Tc(SCH{sub 2}C{sub 6}H{sub 5}){sub 2}(DIARS){sub 2}){sup +}, and cis-(Tc(SC{sub 6}H{sub 5}){sub 2}(DIARS){sub 2}){sup +}, which exhibit a reversible Tc(III/II) redox couple in the range {minus}0.32 to {minus}0.47 V vs. Ag/AgCl. Another redox couple is present in the range {minus}1.22 to {minus}1.70 V; this is ascribed to Tc(II/I) and is reversible only for SR = SCH{sub 2}C{sub 6}H{sub 5} at 20C. At room temperature, chemically irreversible couples are exhibited at ca. +1.0 V for Tc(IV/III).

• DOE Contract Number: FG02-86ER60487
• OSTI ID: 6957500
• Journal Information: Inorganic Chemistry; (United States), Vol. 31:7; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
62 RADIOLOGY AND NUCLEAR MEDICINE
TECHNETIUM COMPLEXES
CHEMICAL PREPARATION
ELECTROCHEMISTRY
BOND ANGLE
BOND LENGTHS
ELECTRIC POTENTIAL
ISOMERS
LIGANDS
MASS SPECTRA
MONOCLINIC LATTICES
MONOCRYSTALS
QUALITATIVE CHEMICAL ANALYSIS
REDOX REACTIONS
TECHNETIUM 99
THIOLS
VOLTAMETRY
X-RAY DIFFRACTION
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
CHEMICAL ANALYSIS
CHEMICAL REACTIONS
CHEMISTRY
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
CRYSTALS
DIFFRACTION
DIMENSIONS
HOURS LIVING RADIOISOTOPES
INTERMEDIATE MASS NUCLEI
INTERNAL CONVERSION RADIOISOTOPES
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
LENGTH
NUCLEI
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
RADIOISOTOPES
SCATTERING
SPECTRA
SYNTHESIS
TECHNETIUM ISOTOPES
TRANSITION ELEMENT COMPLEXES
YEARS LIVING RADIOI
400201* - Chemical & Physicochemical Properties
550604 - Medicine- Unsealed Radionuclides in Therapy- (1980-)