Metal-metal multiply-bonded complexes of technetium. 3. Preparation and characterization of phosphine complexes of technetium possessing a metal-metal bond order of 3.5
- Los Alamos National Laboratory, NM (United States)
Two new ditechnetium complexes possessing Tc-Tc bonds with a formal bond order of 3.5 have been prepared in high yield. Mild chemical oxidation of Tc{sub 2}Cl{sub 4}(PMe{sub 2}Ph){sub 4} with ferrocenium hexafluorophosphate in acetonitrile produces [Tc{sub 2}Cl{sub 4}(PMe{sub 2}Ph){sub 4}][PF{sub 6}] (1) in 82% yield. One-electron oxidation of Tc{sub 2}Cl{sub 4}(PMe{sub 2}Ph){sub 4} by ferrocenium hexafluorophosphate in the presence of ppnCl (ppn = bis(triphenylphosphine)iminium) yielded the neutral compound Tc{sub 2}Cl{sub 5}(PMe{sub 2}Ph){sub 3} (2) in 89% yield. Both species are paramagnetic, as evidenced by EPR spectroscopy, and possess a {sigma}{sup 2}{pi}{sup 4}{delta}{sup 2}{delta}{sup *} ground state electronic configuration on the basis of structural and spectroscopic data. The solid state structures of three forms of 1 have been investigated by X-ray crystallography together with the structure of 2. Electrochemical studies reveal that both compounds are capable of undergoing a one-electron oxidation and a one-electron reduction to yield the respective Tc{sub 2}{sup 6+} and Tc{sub 2}{sup 4+} dinuclear cores. IR, EPR, and UV-vis spectroscopic data are presented for compounds 1 and 2.
- OSTI ID:
- 263748
- 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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