Inter-ligand reactions: in situ formation of new polydentate ligands

Two ligands have been synthesized by derivatisation of cyanuric chloride: 6-(diethylamino)-2,4-disulfanyl-1,3,5-triazine (H2SSta) 1 and 6-(diethylamino)-2-hydroxo-4-sulfanyl-1,3,5-triazine (H2OSta) 2 have been characterised by X-ray crystallography, which shows intermolecular hydrogen bonding in the solid state, leading to dimers of 1 and ribbons of 2. On reaction with metal salts both ligands undergo oligomerisation reactions. Compound 1 reacts with nickel chloride to form a mononuclear complex, [Ni{(Sta)S(S2ta)}] 3. In 3 two triazine ligands have reacted, to form a tetradentate ligand in which two triazine rings are bridged by a sulfur group, with a co-ordinated disulfide group present on one ring and a co-ordinated thiolate on the second. Compound 2 reacts with cobalt(II) chloride to form a cage complex, [Co6NaO(OStaH)7{S(Ota)2}2(O2CPh)2(H2O)2] 4. This complicated structure contains two polydentate ligands formed by linking triazine groups through a bridging sulfur. The cage contains four cobalt(II) and two cobalt(III) sites which are assigned by bond length considerations. The compound [Co(OSta)3] 5 co-crystallises with 4, and its structure has also been determined.