Treatment of a thf solution of trans-[ReCl(N2)(dppe)2] with an excess of NCSiMe3 in sunlight led to the formation of trans-[ReCl(CNSiMe3)(dppe)2] 1 in which the trimethylsilyl isocyanide ligand undergoes desilylation by acid or MeOH to give the aminocarbyne trans-[ReCl(CNH2)(dppe)2]A 2 (A = BF4 or Cl) upon treatment with an excess of HBF4 or HCl or the isocyanide trans-[ReCl(CNH)(dppe)2] 3 upon treatment with a stoichiometric amount of HCl or with MeOH. Complexes 2 convert into 3 by reaction with [NBu4]OH or NEt3 (a more convenient route for 3 than the above), and conversely are obtained from the reaction of 3 with HBF4 or HCl. Anodic controlled potential electrolysis of a solution of 2 (A = BF4) in 0.2 mol dm−3 [NBu4][BF4]–NCMe, until the consumption of 2 F mol−1, resulted in complete deprotonation of the aminocarbyne ligand to give the cyano-complex trans-[ReCl(CN)(dppe)2][BF4] 4 which, upon hydrogen abstraction from the electrolytic medium, converts into the isocyanide compound 3+ isolated as trans-[ReCl(CNH)(dppe)2][BF4]·2[NBu4][BF4]. The detailed syntheses and spectroscopic properties of all these complexes are reported, as well as the crystal structures of 1 and 3, and are discussed in terms of electronic and stereochemical properties of the ligands and binding metal centres.
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