The preparation and reactions of trihaolgeno(alkanonitrile)bis(triphenylphosphine)rhenium(III) complexes

Abstract

The monomeric rhenium(III) complexes, ReX₃(RCN)(PPh₃)₂(R = alkyl; X = Cl or Br), have been prepared in high yield by heating trans-ReOX₃(PPh₃)₂ with triphenylphosphine and an alkanonitrile; other monomeric Re(III) complexes may be obtained from them by ligand substitution, while aerial oxidation gives ReOCl₃(PPh₃O)PPh₃. The nitrile complexes are oxidised rapidly by halogenated compounds of the type R′CY₃(R′= any group; Y = Cl or Br) to ReX₃Y(PPh₃)₂ or ReX₂Y₂(PPh₃)₂. The properties and structures of the new compounds and the mechanisms of the reactions are discussed.