Synthesis, Spectroscopic and Structural Aspects of Mono‐ and Diorganothallium(III) Complexes of 2, 6‐Diacetylpyridine Bis(thiosemicarbazone) (H2DAPTSC) — A New Coordination Mode of the HDAPTSC— Anion

Abstract

AbstractThe reaction of 2, 6‐diacetylpyridine bis(thiosemicarbazone) (H2DAPTSC) with dimethylthallium hydroxide yielded the complexes [(TlMe2)2(DAPTSC)] and [TlMe2(HDAPTSC)]. The structure of [TlMe2(HDAPTSC)], determined by X‐ray diffractometry, exhibits a hitherto unknown coordination mode of the HDAPTSC— anion in which its deprotonated thiosemicarbazone chain coordinates one metal atom through its sulphur and hydrazinic N atoms while a second metal atom is weakly coordinated through the S atom of the undeprotonated thiosemicarbazone chain. Each thallium atom is coordinated in both ways, with the result that the [TlMe2(HDAPTSC)] units are linked in infinite helical chains in the direction of the b axis.When reacting with diphenylthallium(III) hydroxide, H2DAPTSC induced a dephenylation process which led to the monophenylthallium(III) complex [TlPh(DAPTSC)]. Recrystallization from acetone yielded crystals of [TlPh(DAPTSC)]·C3H6O in which X‐ray diffractometry showed DAPTSC2— to be pentadentate, coordinating through its sulphur, azomethine N and pyridine N atoms.The 1H, 13C and 205Tl NMR data of [TlPh(DAPTSC)] indicate that its solid state molecular structure persists in DMSO solution, while those of [TlMe2(HDAPTSC)] indicate rapid alternation between coordination of the metal atom to one of the HDAPTSC— thiosemicarbazone chains and its coordination to the other.