Alkylation of cyanide at [NBu4]trans-[Re(CN) 2(Ph2PCH2CH2PPh2) 2]. Syntheses and properties of derived isocyanide complexes and X-ray structure of trans-[Re(CNEt) 2(Ph2PCH2CH2PPh2) 2][PF6]

Article abstract of DOI:10.1016/0022-328X(95)05956-P

The reaction of RI (R = Me, Et or Pr) or [Et₃O][PF₆] with [NBu₄]trans-[Re(CN)₂(dppe)₂] (dppe = Ph₂PCH₂CH₂PPh₂) affords the diisocyanide complexes trans-[Re(CNR)₂(dppe)₂]A (R = Me, A = I; R = Pr, A = I₃; R = Et, A = PF₆), whereas trans-[Re(CNH)(CNSiMe₃)(dppe)₂]CF₃SO₃ is obtained from the reaction with Me₃SiO₃SCF₃. The X-ray crystal structure of trans-[Re(CNEt)₂(dppe)₂][PF₆] was determined. The redox properties of the compounds were studied by cyclic voltammetry and controlled potential electrolysis, and are discussed in terms of the electronic properties of the metal centres and ligands.