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Title: Technetium bis(. mu. -oxo) dimers of 1,4,7-triazacyclononane-N,N prime N, double prime -triacetate (TCTA). Synthesis and characterization of (TCTA)Tc(. mu. -O) sub 2 Tc(TCTA) sup n- (n = 2,3) and the crystal structure of Ba sub 2 (TCTA)Tc(. mu. -O) sub 2 Tc(TCTA)(ClO sub 4 )ter dot 9H sub 2 O

Abstract

The mixed-valence technetium(III/IV) bis({mu}-oxo) dimer ((TCTA)Tc({mu}-O){sub 2}Tc(TCTA)){sup 3{minus}} (1; TCTA = 1,4,7-triazayclononane-N,N{prime},N{double prime}-triacetate) has been prepared as its sodium and barium salts. This complex undergoes a reversible on-electron oxidation with potassium persulfate to form ((TCTA)Tc({mu}-O){sub 2}Tc(TCTA)){sup 2{minus}} (2). Both complexes have been characterized by elemental analysis, infrared, UV/visible, and resonance Raman spectroscopy, and fast atom bombardment mass spectrometry. A crystal structure analysis of the Tc(III/IV) dimeter Ba{sub 2}((TCTA)Tc({mu}O){sub 2}Tc(TCTA))(ClO{sub 4}){center dot}9H{sub 2}O (1c) reveals that the two Tc atoms are linked by a planar Tc({mu}-O){sub 2}Tc ring. One TCTA ligand binds to each Tc through an N{sub 3}O donor set, and one of the acetate groups from each ligand bridges the two metal atoms. Resonance Raman spectra of complexes 1 and 2 were obtained by irradiation at 514.5 nm; strong bands assigned to the four-membered Tc({mu}-O){sub 2}Tc ring and the metal-metal multiple bond were seen. The aqueous electrochemistry of the compounds confirms that they are related by a reversible one-electron wave. The Tc(III/IV) dimer 1 represents the first fully characterized Tc-(amino carboxylate) complex in an oxidation state lower than +4. Evidence for the existence of other Tc(III/IV) bis({mu}-oxo) dimers of this type with amino carboxylate ligands such as EDTA andmore » NTA is presented. 23 refs., 3 figs., 4 tabs.« less

Authors:
; ;  [1]
  1. Massachusetts Institute of Technology, Cambridge (USA)
Publication Date:
OSTI Identifier:
7170711
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (USA)
Additional Journal Information:
Journal Volume: 28:20; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACETATES; SYNTHESIS; BARIUM COMPLEXES; CHLORINE COMPOUNDS; CYCLOALKANES; ORGANIC NITROGEN COMPOUNDS; OXYGEN COMPOUNDS; TECHNETIUM COMPLEXES; CRYSTAL STRUCTURE; EXPERIMENTAL DATA; ALKALINE EARTH METAL COMPLEXES; ALKANES; CARBOXYLIC ACID SALTS; COMPLEXES; DATA; HALOGEN COMPOUNDS; HYDROCARBONS; INFORMATION; NUMERICAL DATA; ORGANIC COMPOUNDS; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties

Citation Formats

Linder, K E, Dewan, J C, and Davison, A. Technetium bis(. mu. -oxo) dimers of 1,4,7-triazacyclononane-N,N prime N, double prime -triacetate (TCTA). Synthesis and characterization of (TCTA)Tc(. mu. -O) sub 2 Tc(TCTA) sup n- (n = 2,3) and the crystal structure of Ba sub 2 (TCTA)Tc(. mu. -O) sub 2 Tc(TCTA)(ClO sub 4 )ter dot 9H sub 2 O. United States: N. p., 1989. Web. doi:10.1021/ic00319a014.
Linder, K E, Dewan, J C, & Davison, A. Technetium bis(. mu. -oxo) dimers of 1,4,7-triazacyclononane-N,N prime N, double prime -triacetate (TCTA). Synthesis and characterization of (TCTA)Tc(. mu. -O) sub 2 Tc(TCTA) sup n- (n = 2,3) and the crystal structure of Ba sub 2 (TCTA)Tc(. mu. -O) sub 2 Tc(TCTA)(ClO sub 4 )ter dot 9H sub 2 O. United States. doi:10.1021/ic00319a014.
Linder, K E, Dewan, J C, and Davison, A. Wed . "Technetium bis(. mu. -oxo) dimers of 1,4,7-triazacyclononane-N,N prime N, double prime -triacetate (TCTA). Synthesis and characterization of (TCTA)Tc(. mu. -O) sub 2 Tc(TCTA) sup n- (n = 2,3) and the crystal structure of Ba sub 2 (TCTA)Tc(. mu. -O) sub 2 Tc(TCTA)(ClO sub 4 )ter dot 9H sub 2 O". United States. doi:10.1021/ic00319a014.
@article{osti_7170711,
title = {Technetium bis(. mu. -oxo) dimers of 1,4,7-triazacyclononane-N,N prime N, double prime -triacetate (TCTA). Synthesis and characterization of (TCTA)Tc(. mu. -O) sub 2 Tc(TCTA) sup n- (n = 2,3) and the crystal structure of Ba sub 2 (TCTA)Tc(. mu. -O) sub 2 Tc(TCTA)(ClO sub 4 )ter dot 9H sub 2 O},
author = {Linder, K E and Dewan, J C and Davison, A},
abstractNote = {The mixed-valence technetium(III/IV) bis({mu}-oxo) dimer ((TCTA)Tc({mu}-O){sub 2}Tc(TCTA)){sup 3{minus}} (1; TCTA = 1,4,7-triazayclononane-N,N{prime},N{double prime}-triacetate) has been prepared as its sodium and barium salts. This complex undergoes a reversible on-electron oxidation with potassium persulfate to form ((TCTA)Tc({mu}-O){sub 2}Tc(TCTA)){sup 2{minus}} (2). Both complexes have been characterized by elemental analysis, infrared, UV/visible, and resonance Raman spectroscopy, and fast atom bombardment mass spectrometry. A crystal structure analysis of the Tc(III/IV) dimeter Ba{sub 2}((TCTA)Tc({mu}O){sub 2}Tc(TCTA))(ClO{sub 4}){center dot}9H{sub 2}O (1c) reveals that the two Tc atoms are linked by a planar Tc({mu}-O){sub 2}Tc ring. One TCTA ligand binds to each Tc through an N{sub 3}O donor set, and one of the acetate groups from each ligand bridges the two metal atoms. Resonance Raman spectra of complexes 1 and 2 were obtained by irradiation at 514.5 nm; strong bands assigned to the four-membered Tc({mu}-O){sub 2}Tc ring and the metal-metal multiple bond were seen. The aqueous electrochemistry of the compounds confirms that they are related by a reversible one-electron wave. The Tc(III/IV) dimer 1 represents the first fully characterized Tc-(amino carboxylate) complex in an oxidation state lower than +4. Evidence for the existence of other Tc(III/IV) bis({mu}-oxo) dimers of this type with amino carboxylate ligands such as EDTA and NTA is presented. 23 refs., 3 figs., 4 tabs.},
doi = {10.1021/ic00319a014},
journal = {Inorganic Chemistry; (USA)},
issn = {0020-1669},
number = ,
volume = 28:20,
place = {United States},
year = {1989},
month = {10}
}