The reaction of (Bu 4N)[TcOCl 4] in methanol with 1-acetyl-2-phenylhydrazine, followed by 1,2-bis(diphenylphosphino)ethane (DPPE) gives the green technetium(V) phenylimido complex [TcCl 3(NPh)(DPPE)]. The IR spectrum of this complex shows a characteristic peak at 1110 cm -1 which is assigned to v(TcN) from the linearly coordinated phenylimido unit. The 1H NMR spectrum shows a pair of coupled multiplets at 3.1 and 3.6 ppm from the aliphatic protons plus a series of six multiplets between 6.5 and 8.1 ppm from the aromatic protons of the bidentate phosphine ligand and imido-phenyl groups. The positive mode fast atom bombardment mass spectrum displays a peak at 695 m/ z which corresponds to the protonated patent molecule. Also, a peak at 658 m/ z corresponds to the fragment generated from the loss of one chloride from the neutral patent molecule. The X-ray crystal structure shows a facial arrangement of chloride ligands, with a TcN bond length of 1.687 Å and a TcNC bond angle of 175.7° indicative of sp hybridization of the linearly coordinated phenylimido unit. Crystal data for TcCl 3P 2NC 32H 29: monoclinic space group Pc (No. 7), a=11.177(2), b=10.912(2), c=14.056(2) Å, β=108.34(1)°, V=1627.3(5) Å 3, with D calc=1.414 g cm −3 to give Z=2. Structure solution based on 3069 reflections converged at R=0.051, R w=0.072, GOF=2.32. The analogous reaction with triphenylphosphine gives the previously reported Tc(V) phenylimido complex [TcCl 3(NPh)(PPh 3) 2]. This Tc(V) phenylimido complex reacts with pyridine in methanol to give the mixed ligand complex [TcCl 3(NPh)(PPh 3)(NC 5H 5)]. The positive mode FAB mass spectrum of this complex shows fragments which correspond to the sodium adducts of the neutral molecule minus one chloride ligand, (Na)[TcCl 2(NPh)(PPh 3)(C 5H 5N)] + at 624 m/ z, and the molecule minus two chloride ligands, (Na)[TcCl(NPh)(PPh 3)(C 5H 5N)] + at 589 m/ z. Also present in the mass spectrum are peaks which correspond to the fragments [TcCl 3(PPh 3)(C 5H 5N)] + at 545 m/ z and [TcCl 2(PPh 3)(C 5H 5N)] + at 510 m/ z. The IR spectrum of this complex shows an absorption at 1090 cm −1 which is assigned to v(TcN) from the linearly coordinated phenylimido unit.