The tetradentate, neutral disulfide [bis(thioether)] ligand non-oxo V'" complex [V(S'N'O),J 2, derived from the Schiff 1 ,b-bis(o-pyridyl)-2,4-dithiahexane, NSSN, reacts with base HS' "OH, where 0 and S' are phenolate and thiophe-[VCI2(tmeda),] to form the octahedral (all-cis; C2,-symmetric) nolate functions, respectively, and N' is the Schiff base (enacomplex [VCl,(NSSN)] 1, the first low-valent vanadium com-mine) nitrogen. Complex 2, with the ligands in a distorted plex in which the thio functions