Tetrathiafulvalenes. XIX. Synthesis and Properties of Electron Conducting Poly‐Dithiolene Complexes with Ethylene Tetrathiolat and Tetrathiafulvalene Tetrathiolat as Bridge Ligands [1,3]‐Dithiolo[4,5‐d]‐1,3‐dithiol‐2,5‐dione 7 and 5‐(5‐oxo[1,3]‐dithiolo[4,5–d]1,3‐dithiole‐2‐ylidene)[1,3]‐dithiolo[4,5–d]1,3–dithiol‐2‐one 8 were synthesised from 1,3‐dithiole‐2‐thione‐4,5‐dithiolat. The ligands react with salts of iron, cobalt, nickel, palladium, platinum and copper to give the polymer complexes 22a–g and 23a–e, respectively. Irradiation of 7 in the presence of iron penta‐, dicobalt octa‐ or nickel tetracarbonyl gives the corresponding dithiolene complexes 21a–c. The amorphous insoluble polymer complexes from types 21, 22, and 23 have been characterised by i.r.‐spectroscopy, susceptibility and conductivity measurements. The nickel complexes have the highest electrical conductivity (σRT ∼ 10−1Ω−1cm−1, pellets) with a very low activation energy (0,045 eV, 100–300 K) A high electron delocalization in the direction of the polymer chain and an easy charge transfer from chain to chain is supposed.

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Die aus den Dithioliumsalzen (I) (X: I, ClO4, BF4) und β‐Naphthol erhältlichen Dithiolmethide (II) sind schwache Elektronendonatoren, die aber [mit Ausnahme des Di(methylmercapto)‐Derivats] im Unterschied zu den Tetrathiafulvalenen nur ein Elektron abgeben.