A survey of methods for synthesizing tetrathioethylenes and a detailed discussion of a highly efficient new method, orthothiooxalate pyrolysis, are given. Syntheses of tetrathiafulvalene and a dihydrotetrathiafulvalene are described. The electrochemistry of representative tetrathioethylenes has been investigated and found to be characterized by two "clean" one-electron oxidations. E°values and the electronic absorption and esr spectra of the radical cations are discussed in relation to electronic and molecular structure. The ultraviolet spectra of tetrathioethylenes and their electrochemical properties can be rationalized by extended Hiickel calculations provided the 3d orbitals of sulfur are included in the basis sets. A search for conventional "electron-rich olefin" chemistry has given negative results. This lack of reactivity in contrast to oxygen and nitrogen analogs can also be rationalized by including d orbitals in the -bonding model.

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