New π-Extended Donors: Synthesis,Characterization, Electrochemical and Electrical Conductivity Studies

A new series of tetrathiafulvalene (TTF) molecules with extended π-system was prepared by using a Wittig reaction to generate the TTF key. The process of deprotection-alkylation of thiolates provided access to a wide variety of molecules. The study of their reducing power was carried out by cyclic voltammetry. Charge transfer complexes have also been chemically prepared by using TCNQ as an electron acceptor; the electrical conductivity of their compressed powders shows insulator behavior. The IR spectra of the TCNQ salts were recorded and used to characterize and estimate the degree of charge transfer of these complexes.

GRAPHICAL ABSTRACT      

Synthesis and electrochemical studies of ferrocene-dithiafulvalenes (Fc-DTF) and 1,1′-bis(dithiafulvalenyl)ferrocene (DTF-Fc-DTF). An approach towards new conducting organic materials

Novel π-conjugated donor compounds based on the strong electron-donating ferrocene moiety and dithiafulvalene donors exhibited increased electron donor ability. The ferrocenylketones 4a,b, 5, 8 and 9 were synthesized via described methods, and allowed to react with 2-dimethoxyphosphinyl-1,3-benzodithiole (13) in the presence of n-BuLi at −78°C in dry THF to afford the corresponding ferrocene-dithiafulvalenes 14a,b, 18, 19 and 1,1′-bis(benzo-1,3-dithiol-2-ylidene)ethyl]ferrocene (15). Electrochemical properties of these new donor compounds were studied using cyclic voltammetry (CV) and UV-Vis spectra. CV and absorption spectra of the new compounds were studied in comparison with ferrocene (6) and dibenzo-tetrathiafulvalene DB-TTF 3. Two-electron and three-electron redox behaviors were observed as two waves. The absorption spectra showed a red-shift with a slight increase in the absorption intensities.     

Comonomer effects with high-activity titanium- and vanadium-based catalysts for ethylene polymerization

High-activity titanium- and vanadium-based catalysts for ethylene polymerization frequently show an increase in reaction rate in the presence of an α-olefin. The magnitude of this increase depends on the specific α-olefin. The results show propylene > 1-butene > 1-hexene in increasing initial reaction rates. Addition of certain electron-donor compounds to these catalysts can lower the magnitude of the comonomer effect and, in some cases, totally eliminate such an effect. Among the classes of electron-donor compounds examined were ether-alcohols, ether-esters, amino-alcohols, alkoxysilanes, siloxanes, and phosphine oxides. Reaction kinetics show that the presence of a comonomer can influence the kinetic order of the reaction. These results can be interpreted using a mechanistic model involving two vacant coordination positions at the active sites. In this model electron donors and comonomers are viewed as Lewis-base ligands which influence features of chain propagation and chain termination. As Lewis-base ligands, the comonomers can also increase the number of active sites available for polymerization. Catalyst deactivation following the initial comonomer rate increase is believed to be caused by reaction with the Lewis bases (α-olefin included) in the system and by possible reduction in the oxidation state of the metal centers. The most acidic metal centers activated by the comonomer are most reactive to Lewis bases and deactivate most rapidly. Veratrole (1,2-dimethoxybenzene) can be employed as a probe for estimating the number of bis-vacant coordination sites in vanadium-based catalysts. Addition of low levels of veratrole led to significant deactivation of the vanadium-based catalyst. © 1993 John Wiley & Sons, Inc.