[Tc(NO)Cl(Cp)(PPh3)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

Reactions of the chiral organometallic technetium(I) compound [Tc(NO)Cl(Cp)(PPh3)] (1 a) with phosphines and alkynes give unexpected products such as the dimeric cation [{Tc(NO)(Cp)(PPh3)}2Cl]+ (4) or the Fischer‐type carbene [Tc(NO)(Cp)(PPh3){C(OR)C2H4PPh3}]2+ (5). Both products could be isolated a...

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Bibliographic Details
Published in:European journal of inorganic chemistry 2021-10, Vol.2021 (37), p.3812-3818
Main Authors: Abdulkader, Abdullah, Hagenbach, Adelheid, Abram, Ulrich
Format: Article
Language:English
Subjects:
Alkynes
Carbenes
Dimers
High temperature
Inorganic chemistry
Organometallics
Phosphines
Phosphonio ligands
Technetium
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Summary:Reactions of the chiral organometallic technetium(I) compound [Tc(NO)Cl(Cp)(PPh3)] (1 a) with phosphines and alkynes give unexpected products such as the dimeric cation [{Tc(NO)(Cp)(PPh3)}2Cl]+ (4) or the Fischer‐type carbene [Tc(NO)(Cp)(PPh3){C(OR)C2H4PPh3}]2+ (5). Both products could be isolated as PF6− salts and studied by spectroscopic methods and X‐ray diffraction. While [Tc(NO)(Cp)(PMe3)(PPh3)](PF6) (2PF6) can be obtained from 1 a, PMe3 and Ag(PF6) under ambient conditions, the synthesis of the corresponding bis‐triphenylphosphine complex [Tc(NO)(Cp)(PPh3)2](PF6) (3PF6) requires high temperatures and long reaction times. The products are stable in air. Stable technetium(I) complex cations with Fischer‐type carbene ligands are formed during reactions of [Tc(NO)(Cp)Cl(PPh3)] with trimetylsilyl propyne and Ag(PF6) in CH2Cl2/‐alcohol mixtures, while the dimeric compound [{Tc(NO)(Cp)(PPh3)}2Cl]+ is formed, when no other ligand is provided.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.202100521