SYNTHESIS AND CHARACTERIZATION OF TECHNETIUM(III) AND TECHNETIUM(II) COMPLEXES WITH MIXED PHOSPHINE-DONOR, CHLORIDE-DONOR, AND NITROGEN-DONOR LIGANDS - X-RAY CRYSTAL-STRUCTURE OF TCCL3(PPH3)(BPY)

The synthesis and characterization of Tc(III) complexes of the types TcCl3(PMe2Ph)(LL) and TcCl2(PMe2Ph)2(LL)+, the neutral Tc(II) series TcCl2(PMe2Ph)2(LL), and the Tc(II) complex TcCl(PMe2Ph)3(bpy)+ are reported (LL = 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 2,2′-bipyrimidine (bpm)). The Tc(III) complexes exhibit contact-shifted lH NMR spectra with relatively narrow line widths; the Tc(II) species give less well-defined spectra. The electrochemistry of these complexes is discussed as well. An X-ray structure determination of TcCl3(PPh3)(bpy) was performed. Crystal data for C28H23Cl3N2PTc: monoclinic, space group = P2l/n, a = 10.980 (2) Å, b = 24.336 (5) Å, c = 10.172 (2) Å, β = 106.89 (1)°, V = 2600.9 (8) Å3 to give Ζ = 4. Structure solution and refinement based on 4366 reflections converged at R = 0.057 and Rw = 0.074. © 1990, American Chemical Society. All rights reserved.