ELECTROCHEMICAL PREPARATION OF ISOCYANIDE COMPLEXES OF LOW-VALENT PLATINUM CONTAINING A METAL–METAL BOND
The potentiostatic reduction of cis-PtCl2(RNC)2 (3a:R = 2,4-t-Bu2-6-MeC6H2; 3b: R = 2,4,6-t-Bu3C6H2; 3c: R = 2,6-Me2C6H3) were carried out on a mercury pool electrode in CH3CN. The one-electron reduction (96.5 kC/mol) of 3a and 3b gave [PtCl(RNC)2]2 (4a and 4b). An X-ray analysis of 4a showed that the two PtCl(RNC)2 planes jointed by a Pt-Pt bond were perpendicular. The two-electron reductions (2×96.5 kC/mol) of 3a and 3b gave Hg[Pt3(RNC)6]2 and Pt3(RNC)6, respectively. Electrolysis of 3c gave only Hg[Pt3(2,6-MeC6H3NC)6]2.