Synthesis and characterization of mixed-ligand technetium(II) complexes containing halides, phosphines, and either 2,2 prime -bipyridine, 1,10-phenanthroline, or 2,2 prime :6 prime ,2 double prime -terpyridine. X-ray crystal structures of cis(Cl),trans(P)-(TcCl sub 2 (P(CH sub 3 ) sub 2 C sub 6 H sub 5 ) sub 2 (phen)) and trans(P)-(TcBr(P(CH sub 3 ) sub 2 C sub 6 H sub 5 ) sub 2 (terpy))SO sub 3 CF sub 3 sup 1

Journal Article · Wed Oct 04 00:00:00 EDT 1989 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00319a031· OSTI ID:7246154

Wilcox, B E; Ho, D M; Deutsch, E ^[1]

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1. Univ. of Cincinnati, OH (USA)

Technetium(II) complexes of the general formula cis(X),trans(P)-(TcX{sub 2}(PR{sub 2}R{prime}){sub 2}L), where X = Cl or Br, PR{sub 2}R{prime} = dimethylphenylphosphine or ethyldiphenylphosphine, and L = 2,2{prime}-bipyridine (bpy) or 1,10-phenanthroline (phen), have been synthesized and characterized. They are prepared by replacement of one halide and one phosphine ligand of mer-TcX{sub 3}(PR{sub 2}R{prime}){sub 3} by the bidentate L ligand in refluxing ethanol, followed by reduction to the Tc(II) oxidation state and precipitation from solution by the addition of aqueous hydroxide. Additionally, related technetium(II) complexes of the general formula trans(P)-(TcX(PR{sub 2}R{prime}){sub 2}(terpy)){sup +}, where terpy = 2,2{prime}:6{prime},2{double prime}-terpyridine, have been synthesized and characterized. They are prepared by terpy substitution onto and displacement of one phosphine and two halide ligands from mer-TcX{sub 3}(PR{sub 2}R{prime}){sub 3} in refluxing ethanol with concomitant reduction of Tc(III) to Tc(II). Evidence suggests a two-step synthetic process wherein the terpy ligand first displaces one halide and one phosphine moiety to form a Tc(III) complex in which terpy functions as a bidentate ligand, followed by subsequent displacement of the second halide ligand with coordination of the third heterocyclic nitrogen of the terpy ligand and reduction to the Tc(II) state. All of the complexes have been characterized by elemental analyses of prototypes, by UV-visible spectrophotometry, and by fast atom bombardment mass spectrometry in the positive ion mode. 28 refs., 3 figs., 7 tabs.

• OSTI ID: 7246154
• Journal Information: Inorganic Chemistry; (USA), Vol. 28:20; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BIPYRIDINES
SYNTHESIS
CHLORINE COMPOUNDS
FLUORINE COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHENANTHROLINES
PHOSPHINES
SULFITES
TECHNETIUM COMPLEXES
CRYSTAL STRUCTURE
EXPERIMENTAL DATA
MOLECULAR STRUCTURE
AROMATICS
AZAARENES
AZINES
COMPLEXES
DATA
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
PHOSPHORUS COMPOUNDS
PYRIDINES
SULFUR COMPOUNDS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties