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Synthesis, spectroscopy, and structural characterization of neutral seven-coordinate technetium xanthate complexes. X-ray structure of (Tc(PPh sub 3 )(S sub 2 COC sub 4 H sub 9 ) sub 3 ), a capped octahedral technetium(III) complex

Journal Article · · Inorganic Chemistry; (USA)
DOI:https://doi.org/10.1021/ic00326a019· OSTI ID:6835185
;  [1]; ;  [2]; ;  [3]
  1. Massachusetts Institute of Technology, Cambridge (USA) Harvard Medical School, Boston, MA (USA)
  2. Massachusetts Institute of Technology, Cambridge (USA)
  3. Harvard Medical School, Boston, MA (USA)

Reaction of (Bu{sub 4}N)(TcOCl{sub 4}) with triphenylphosphine and an excess of potassium xanthate yields neutral complexes of the general formula (Tc(PPh{sub 3})(S{sub 2}COR){sub 3}) (R = ethyl, isopropyl, n-butyl, neopentyl). The infrared spectra show a single C{double bond}S absorption from the exclusively bidentate xanthate ligands. The fast-atom-bombardment mass spectral results show the parent ions and a complex fragmentation pattern that includes two sulfido species. The x-ray structure of (Tc(PPh{sub 3})(S{sub 2}COBu{sup n}){sub 3}) confirms the unusual seven-coordinate, capped octahedral geometry, with the technetium and phosphorus atoms each sitting on 3-fold axes and a single crystallographically unique n-butyl xanthate ligand. Crystal data for C{sub 33}H{sub 42}O{sub 3}PS{sub 6}Tc is reported. The {sup 1}H NMR spectra show that the 3-fold molecular symmetry is maintained in solution, with a single set of C-H absorptions from the three xanthate ligands. The {sup 99}Tc NMR resonances of these complexes fall in the Tc(V) region and are the first technetium complexes with sulfur ligation to be so characterized. 16 refs., 3 figs., 4 tabs.

OSTI ID:
6835185
Journal Information:
Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 29:1; ISSN 0020-1669; ISSN INOCA
Country of Publication:
United States
Language:
English