[TcI(NO)X(Cp)(PPh3)] Complexes (X– = I–, I3 –, SCN–, CF3SO3 –, or CF3COO–) and Their Reactions

Reactions of [Tc­(NO)­Cl­(Cp)­(PPh3)] with a series of monodentate ligands X– (X– = I–, I3 –, F3CSO3 –, CF3COO–, or SCN–) result in a ready replacement of the chlorido ligand and the formation of complexes of the general composition [Tc­(NO)­X­(Cp)­(PPh3)]. Technetium retains its oxidation state “+1...

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Bibliographic Details
Published in:Organometallics 2019-11, Vol.38 (22), p.4471-4478
Main Authors: Ackermann, Janine, Abdulkader, Abdullah, Scholtysik, Clemens, Jungfer, Maximilian Roca, Hagenbach, Adelheid, Abram, Ulrich
Format: Article
Language:English
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Summary:Reactions of [Tc­(NO)­Cl­(Cp)­(PPh3)] with a series of monodentate ligands X– (X– = I–, I3 –, F3CSO3 –, CF3COO–, or SCN–) result in a ready replacement of the chlorido ligand and the formation of complexes of the general composition [Tc­(NO)­X­(Cp)­(PPh3)]. Technetium retains its oxidation state “+1” and its pseudotetrahedral coordination environment. [Tc­(NO)­(SCN)­(Cp)­(PPh3)] is the first technetium complex with an S-coordinated SCN– ligand. The complexes are stable as solids. In solution, however, a slow isomerization of the thiocyanato compound into the thermodynamically more stable isothiocyanato species is observed, while solutions of [Tc­(NO)­(I3)­(Cp)­(PPh3)] undergo an internal oxidation under formation of the technetium­(II) complex [Tc­(NO)­(I)2(Cp)]. All products were characterized by elemental analysis, NMR and IR spectroscopy, and X-ray structure analysis. Particularly, 99Tc NMR spectroscopy proved to be a valuable method for these types of technetium­(I) compounds.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.9b00620