[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)}(2)Cl](+) (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) (2PF(6)) 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) (3PF(6)) requires high temperatures and long reaction times. The products are stable in air.