The reduction of the mononitrosyl Re (II) salt [NMe4] 2 [ReCl5 (NO)](1) with zinc in acetonitrile afforded the Re (I) dichloride complex [ReCl2 (NO)(CH3CN) 3](2). Subsequent ligand substitution reactions with PCy3, PiPr3 and P (p-tolyl) 3 afforded the bisphosphine Re (I) complexes [ReCl2 (NO)(PR3) 2 (CH3CN)](3, R= Cy a, iPr b, p-tolyl c) in good yields. The acetonitrile ligand in 3 is labile, permitting its replacement with H2 (1 bar) to afford the ...