Thiolato-technetium complexes. 3. Synthesis and x-ray structural studies on the geometrical isomers cis- and trans-bis(p-chlorobenzenthiolato)bis(1,2-bis(dimethylphosphino)ethane)technetium(II)

Journal Article · Wed May 03 00:00:00 EDT 1989 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00308a020· OSTI ID:5064402

Konno, Takumi; Deutsch, E ^[1]; Heeg, M J ^[2]

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

The reaction of trans-(Tc{sup v}(OH)(O)(DMPE){sub 2}){sup 2+} with excess p-chorobenzenethiol and a small amount of base produces both cis and trans isomers of the air-stable arenethiolato-Tc(II) complex (Tc(SC{sub 6}H{sub 4}-p-Cl){sub 2}(DMPE){sub 2}). The geometries of these complexes are confirmed by x-ray crystallography, and the crystal data are reported. The cis isomer is considerably more stable than the trans; trans {yields} cis isomerization occurs with a half-life of about 74 min in dichloromethane at room temperature. The cis isomer exhibits a reversible Tc(III/II) redox couple at -0.182 V vs Ag/AgCl and a nonreversible Tc(II/I) couple at about -0.99 V vs Ag/AgCl. The remarkable stability of cis-(Tc(SC{sub 6}H{sub 4}-p-Cl){sub 2}(DMPE){sub 2}) in the Tc(II) oxidation state and in the cis geometry is discussed in terms of the electronic and steric properties of the aryl substituent. 33 refs., 4 figs., 6 tabs.

• OSTI ID: 5064402
• Journal Information: Inorganic Chemistry; (USA), Vol. 28:9; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ORGANIC PHOSPHORUS COMPOUNDS
CRYSTAL STRUCTURE
ORGANIC SULFUR COMPOUNDS
ORGANOMETALLIC COMPOUNDS
TECHNETIUM COMPLEXES
CHEMICAL PREPARATION
EXPERIMENTAL DATA
ISOMERIZATION
MOLECULAR STRUCTURE
CHEMICAL REACTIONS
COMPLEXES
DATA
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties