A New Sulfur-Rich Rhenium(III) Complex, Re(S2CC6H5)(S3CC6H5)2, and Seven-Coordinate Complexes Formed by Reversible Sulfur Abstraction Reactions, Re(S2CC6H5)3(PPh3) and [Re(S2CC6H5)3(CN)]-

A novel sulfur-rich rhenium(III) diamagnetic, mononuclear complex, Re(S2CC6H5)(S3CC6H5)2, has been isolated from the induced internal redox reaction of tetraethylammonium tetrathioperrhenate(VII) with dithiobenzoate disulfide. The green six-coordinate octahedral complex displays two reversible one-electron oxidations and undergoes reversible sulfur abstraction with triphenylphosphine or tetraethylammonium cyanide to give purple seven-coordinate [ReL3L‘]n- complexes where L‘ = P(C6H5)3 (n = 0) or CN- (n = 1).