The cationic organoimido-hydrido complexes [ReH 2(NR)(Cyttp)] + where R=NC 6H 4Me- p ( 2), Ph ( 3), Cy ( 4) and Cyttp = Php(CH 2CH 2CH 2PCy 2) 2 were synthesized by reaction of [ReH 2(O) (Cyttp) ]O 3SCF 3 ( 1(Tf)) with the appropriate primary amine. Use of molecular sieves promotes the formation of these rhenium products. 2–4 were shown by 1H NMR spectroscopy to contain two inequivalent, cis hydride ligands. An X-ray diffraction study of 2(PF 6) revealed the presence of distorted mer-Cyttp and the organoimido ligand cis to all three phosphorus atoms. The hydrido ligands were not located. Unlike its oxo-hydrido analogue, 1(SbF 6), 2(Tf) failed to react with CO or SO 2 under comparable, or even more forcing, conditions. However, with anhydrous HCl it afforded ReCl 3(Cyttp), and with NaBH 4, ReH 5(Cyttp).