Structural characterizations of an Re(IV) complex [ReCl(4)(OPPh(3))(2)] and of an imino species [ReOCl(2)(PPh(3))(eta-OC(6)H(4)-2-CH=NH)] prepared from the reaction of [ReOCl(3)(PPh(3))(2)] with salicylaldoxime.

The reaction of [ReOCl(3)(PPh(3))(2)] with salicylaldoxime unexpectedly yields [ReCl(4)(OPPh(3))(2)] (1) and [ReOCl(2)(PPh(3))(eta(2)-OC(6)H(4)-2-CH=NH)] (2). The crystal structure of the Re(IV) complex 1 consists of discrete mononuclear units. The Re site is bound to four chlorides and two trans oxygens of the OPPh(3) groups. The crystal structure of 2 is also mononuclear with the geometry of the Re(V) center defined by a terminal oxo-group, two cis chlorides, the phosphorus of the PPh(3), and the nitrogen and oxygen donors of the phenoxyimino ligand [OC(6)H(4)-2-CH=NH](-).