Synthesis, electronic properties, and solid-state structure of [[(tpy)(Me{sub 2}bpy)Tc]{sub 2}({mu}-O)]{sup 4+/2+}
- Los Alamos National Laboratory, NM (United States)
The oxo-bridged technetium(III) polypyridyl complex, [(tpy)(Me{sub 2}bpy)Tc-O-Tc(tpy)(Me{sub 2}bpy)](OTf){sub 4} 1, abbreviated [(N{sub 5}Tc){sub 2}O]{sup 4+}, was prepared from the reaction of TcCl{sub 3}(tpy), TlOTf, and adventitous water. In contrast to other known {mu}-oxo systems of technetium or ruthenium, the cyclic voltammetric data of [(N{sub 5}Tc){sub 2}O]{sup 4+} suggests a relatively weak metal-metal interaction, however the visible absorption spectrum an the apparent magnetic properties suggests that this interaction cannot be completely dismissed. Crystallographic data of 1: triclinic, P1, {alpha}=12.906(2) {Angstrom}, b=14.320(4) {Angstrom}, c = 19.568(2) {Angstrom}, {alpha} = 77.55(1){degrees}, {Beta} = 72.13(1){degrees}, {gamma} = 76.83(2){degrees}, V=3308 {Angstrom}{sup 3}, Z=2. The Tc=O bond lengths are 1.833(6) and 1.830(6) {Angstrom}, and the Tc-O-Tc bond angle is 171.1(3){degrees}. The zinc reduction of 1 results in the two electron reduced oxo-bridged dimer, [(N{sub 5}Tc){sub 2}O]{sup 2+}. Both complexes exhibit intense, low energy bands in the visible region characteristic of {mu}-oxo compounds, and these bands are red shifted by approximately 5000 cnm{sup {minus}1} in the reduced complex.
- OSTI ID:
- 263747
- Journal Information:
- Inorganic Chemistry, Vol. 35, Issue 7; Other Information: PBD: 27 Mar 1996
- Country of Publication:
- United States
- Language:
- English
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