Tris(dimethylphenylphosphine)(dinitrogen)(dithiocarbamato)rhenium complexes and their reactions with hydrogen halides

Abstract

The complexes mer-[Re(S₂CNR₂)(N₂)(PMe₂Ph)₃](I; R = Me or Et) have been prepared from trans-[ReCl(N₂)(PMe₂Ph)₄] and Na[S₂CNR₂]. With an excess of HX (X = Cl or Br) in tetrahydrofuran (thf) solution they give the dihydrido-complexes [ReH₂(S₂CNR₂)X(PMe₂Ph)₃]X, (II), which on treatment with NEt₃ give [ReH(S₂CNR₂)X(PMe₂Ph)₃], (III). Complexes (III) give [ReH(S₂CNR₂)₂(PMe₂Ph)₂], (IV), on reaction with Na[S₂CNR₂]. The spectroscopic properties of these complexes are described, particularly the ¹H n.m.r. spectra which are solvent dependent. The complexes mer-[ Re(L)(N₂)(PMe₂Ph)₃](L = S₂COEt or S₂PPh₂) have also been prepared.