Abstract
[NBu4][trans-Re(CN)2(dppe)2] (1, dppe = Ph2PCH2CH2PPh2) reacted with protic acids (HA = HBF4, CH3CO2H or [Et3NH][BPh4], added in stoichiometric amounts) to give, on protonation of one of the cyano-ligands, the isocyanide complex trans-[Re(CN)(CNH)(dppe)2] 3a, whereas the hydrogen-bonded cyano-adducts trans-[Re(CN·HO2CCF3)2(dppe)2] 4, trans-[Re(CN·HOMe)2(dppe)2] 5 and trans-[Re(CN·HNEt3)2(dppe)2][BPh4] 6 were obtained on treatment of 3a with an excess of CF3CO2H or of 1 with an excess of MeOH or [Et3NH][BPh4], respectively. However, solvent or other molecules can be trapped in the crystal lattice without hydrogen-bond interaction and trans-[Re(CN)2(dppe)2]·2L (L = MeOH 2a or Me2CO 2b) or trans-[Re(CN)2(dppe)2]·NEt37 are formed on attempted recrystallization of 1 from MeOH or Me2CO, or as a side product in the reaction of 1 with [Et3NH][BPh4], respectively. The crystal structures of 2b, 4, 5 and partially that of 2a were also determined and the anodic cyclic voltammetric behaviour (which is shown to distinguish between the CN–H and the hydrogen-bond CN⋯H formations) of the above complexes is described as well as an interpretative theoretical study (by extended Huckel and ab initio methods) of the CN and CNH complexes.
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