ELECTROCHEMICAL FORMATION AND X-RAY STRUCTURE OF THE 5-COORDINATED RUTHENIUM(II) [RUCL(DPPP)2](PF6) COMPLEX

The electrochemical oxidation of trans-chlorohydrido-di-1,3-bis(diphenylphosphino)propaneruthenium(II), [HRua(dPPP)2], Was StUdied at a platinum electrode in dichloromethane containing 0.1 mol/l tetrabutylammonium perchlorate (TBAP). The cyclic voltammogram shows two one-electron oxidation waves corresponding to the formation of Ru(III) and Ru(IV) species. To account for this observation and considering that the pH of the solution decreases during the experiment, an internal reduction of Ru(IV) to Ru(II) is proposed generating the five-coordinated [RuCl(dPPP)2]+ species. The X-ray structure of the [RuCl(dPPP)2](PF6) complex, recrystallized from dichloromethane/diethyl ether was determined and found to have, approximate C2nu symmetry about the metal center.