82741-97-7Relevant academic research and scientific papers
Isocyanide as a ligand on ruthenium(II) ammines
Dozsa,Sutton,Taube
, p. 3997 - 4000 (1982)
A pentaammine-isocyanide complex of Ru(II) is readily prepared by the reaction of Ru(NH3)5H2O2+ with the ligand, but if the contact time is long, a trans-bis(isocyanide) complex results. Measurement of the rate of aquation of the benzyl isocyanide complex Ru(NH3)5C7H7NC2+ compared with earlier measurements for Ru(NH3)62+ shows that C7H7NC (as compared to ammonia) labilizes a trans ammonia by a factor of 40. A similar comparison between Ru(NH3)4(H2O)C7H7NC 2+, now following the replacement of H2O by isn (isonicotinamide), shows that the trans isocyanide (compared to trans ammonia) is slightly delabilizing. The rate of aquation of isn in a trans position is enormously enhanced by isocyanide as compared to ammonia, and the affinity of Ru(II) for isn is much reduced. As determined by cyclic voltammetry, the values of Ef for the couples Ru(NH3)5C7H7NC3+/2+, Ru(NH3)4(H2O)C7H7NC 3+/2+, trans-Ru(NH3)4(C7H7NC) 23+/2+, and trans-Ru(NH3)4(C-HxNC)23+/2+ are 0.79, 0.92, 0.99, and 0.93 V vs. NHE at 25°C.
