An unusual reaction of bis(dimethylglyoximato) complexes: synthesis and characterization of rhodium(III) complexes containing an oxime-imine equatorial moiety

Reaction of Rh(I)dimethylglyoximato monoanion (Hdmg)2 with small cone angle phosphines leads to reduction of one of the four equatorial oximes to an imine group. Four nonequivalent nitrogen atoms in the reaction product (Rh(III)(Hdmg)2,3-butanedione 2-imine 3-oximato (Hbdio)(PR3)2)+ connect the ligands Hdmg and Hbdio to Ru(III). Two phosphines in the trans positions complete the metal coordination sphere. X-ray crystallographic studies help determine the structure of the complexes, and polarographic and cyclic voltammetric studies enable the investigation of the electrochemical properties of the complexes.