Thiolato-technetium complexes. 1. Synthesis and characterization of bis(tertiary diphosphine)technetium(III) complexes containing methanethiolato ligands. Single-crystal structural analyses of trans-(Tc/sup III/(SCH/sub 3/)/sub 2/(DMPE)/sub 2/)CF/sub 3/SO/sub 3/ and trans-(Tc/sup III/(SCH/sub 3/)/sub 2/(DEPE)/sub 2/)PF/sub 6/, where DMPE = 1,2-bis(dimethylphosphino)ethane and DEPE = 1,2-bis(diethylphosphino)ethane

Journal Article · Tue Nov 15 23:00:00 EST 1988 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00296a008· OSTI ID:5761950

Konno, T; Heeg, M J; Deutsch, E

The Tc(III) methanethiolato complexes trans-(Tc(SCH/sub 3/)/sub 2/D/sub 2/)/sup +/, where D is either 1,2-bis(dimethylphosphino)ethane (DMPE) or 1,2-bis(diethylphosphino)ethane (DEPE), have been synthesized and characterized. Preparation of these complexes from (Tc/sup V/(O)(OH)D/sub 2/)/sup 2+/ utilizes excess NaSCH/sub 3/ as reductant and ligand. The x-ray crystal structures of both title complexes are examined, and the crystal parameters are reported. In both structures the Tc atom occupies an inversion center. The visible spectra of these trans-(Tc(SCH/sub 3/)/sub 2/D/sub 2/)/sup +/ complexes in acetonitrile show sulfur-technetium charge-transfer bands at 16,810 and 28,490 cm/sup /minus/1/ for D = DMPE and at 16,610 and 28,830 cm/sup /minus/1/ for D = DEPE. Cyclic voltammetric measurements in N,N-dimethylformamide show two reversible reduction couples corresponding to Tc(III/II) and Tc(II/I) at -0.550 and -1.72 V vs Ag/AgCl for D = DMPE and -0.554 and -1.81 V vs Ag/AgCl for D = DEPE. The absorption spectra and cyclic voltammograms are compared with those of other trans-(TcD/sub 2/X/sub 2/)/sup +/ complexes with X = Cl, Br, -NCS and are discussed in terms of the relative strengths of the /simga/ and /pi/ interactions between Tc and the ligating S and P atoms. 45 refs., 5 figs., 8 tabs.

• Research Organization: Univ. of Cincinnati, OH (USA)
• OSTI ID: 5761950
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:23; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
COMPLEXES
CRYSTAL STRUCTURE
CRYSTALS
DATA
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HOURS LIVING RADIOISOTOPES
INFORMATION
INTERMEDIATE MASS NUCLEI
ISOMERIC TRANSITION ISOTOPES
ISOTOPE APPLICATIONS
ISOTOPES
LABELLED COMPOUNDS
MONOCRYSTALS
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHOSPHORUS COMPOUNDS
PHOSPHORUS FLUORIDES
RADIOISOTOPES
SYNTHESIS
TECHNETIUM 99
TECHNETIUM COMPLEXES
TECHNETIUM ISOTOPES
TRACER TECHNIQUES
TRANSITION ELEMENT COMPLEXES
YEARS LIVING RADIOISOTOPES