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

Treatment of a C222‐vanadyl‐AMP complex (C222 = cryptand‐222, AMP = adenosine monophosphate) with Me2NH in the presence of air yielded centrosymmetric dihydrogen‐decavanadate H2V10O428, sandwiched by two diprotonated C222 molecules. An X‐ray crystal‐structure analysis was performed of this compound with the overall composition [C222(H+)2]2[H2V10O28] · 2 1/2, H2O. Protonation sites in the anion are μ2‐oxygen atoms linking two different vanadium centres. Protonation sites at the cryptand are the nitrogen and/or oxygen atoms of one of the −[CH2]2O[−CH2|2O|CH2]– bridges. The relevance of the compound for the stabilisation and transport of the kinase and phosphatase inhibitor decavanadate by biogenic ionophores is addressed.