ALKYLATION OF CYANIDE AT BU(4)]TRANS-[RE(CN)(2)(PH(2)PCH(2)CH(2)PPH(2))(2)] - SYNTHESES AND PROPERTIES OF DERIVED ISOCYANIDE COMPLEXES AND X-RAY STRUCTURE OF RANS-[RE(CNET)(2)(PH(2)PCH(2)CH(2)PPH(2))(2)][PF6]

The reaction of RI (R = Me, Et or Pr) or [Et(3)O][PF6] with [NBu(4)]tr ans-[Re(CN)(2)(dppe)(2)] (dppe = Ph(2)PCH(2)CH(2)PPh(2)) affords the d iisocyanide complexes trans-[Re(CNR)(2)(dppe)(2)]A (R = Me, A = I; R = Pr, A = I-3; R = Et, A = PF6), whereas trans-[Re(CNH)(CNSiMe(3))(dppe )(2)]CF3SO3 is obtained from the reaction with Me(3)SiO(3)SCF(3). The X-ray crystal structure of trans-[Re(CNEt)(2)(dppe)(2)][PF6] was deter mined. The redox properties of the compounds were studied by cyclic vo ltammetry and controlled potential electrolysis, and are discussed in terms of the electronic properties of the metal centres and ligands.