Access to and reactions of P-functional tetrathiafulvalene derivatives

Abstract

This Ph.D. thesis describes the chemistry of the first P-functional tetrathiafulvalenes; the chlorophosphanyl-substituted TTFs were subjected to a reaction with Galliumtrichloride, as a chloride abstraction reagent, to form the related phosphenium compounds, however, an intramolecular one-electron transfer from readily oxidizable TTF moiety to phosphorus atom, led to the formation of the related biradical dication dimer. chlorophosphanyl-substituted TTFs were also used as precursors to obtain 1,4-dihydro-1,4-diphosphinines being fused to two TTF units via ring-closing reaction; the oxidation of the latter was performed using chalcogens thus yielding in new P(V)/P(V) dichalcogenides. Furthermore, 1,4-bis(diethylamino)-1,4-dihydro-1,4-diphosphinines were subjected to a scrambling reaction followed by reduction to get access to the related 1,4-diphosphinine, but, unfortunately, the desired product could not be isolated. Nevertheless, trapping of in situ formed 1,4-diphosphinine via [4+2]-cycloaddition, using 1-hexene, resulted in the corresponding 1,4-diphosphabarrelene, thus providing indirect evidence for 1,4-diphosphinine. In addition, oligomeric products having TTF units in their main chain were synthesized via ring-closing reaction of doubly-phosphanylated TTFs and desulfurization of 1,3-dithiole-2-thione annulated 1,4-bis(diethylamino)-1,4-dihydro-1,4-diphosphinine. The electrochemical properties of isolated compounds were studied using cyclic voltammetry.