THE PREPARATION AND ELECTROCHEMISTRY OF TECHNETIUM AND RHENIUM COMPLEXES OF 2-(DIPHENYLPHOSPHINO)BENZENETHIOL - THE CRYSTAL AND MOLECULAR-STRUCTURES OF [RE(2-PH2PC6H4S)3] AND [TC(2-PH2PC6H4S)3]

Reaction of a variety of rhenium(III) or (V) precursors with the bidentate (1 -) mixed phosphino-thiol ligand 2-(diphenylphosphino)benzenethiol (DPPBTH) in mildly alkaline methanol leads to the formation of the 16-electron complex [Re(DPPBT)3] (I). With technetium [Tc(DPPBT)3] (II), [TcOCl(DPPBT)2] (III) or [TcN(DPPBT)2] (IV) may be obtained depending on the conditions and starting material. The X-ray crystal and molecular structures of I and II show very similar distortions from ideal geometry due to intraligand interactions. The complexes have been further studied by cyclic voltammetry and UV-vis spectroscopy.