Synthesis of Organometallic Mixed Sulfur-Selenium pi -Acceptor Molecules.

摘要

The relative dianion, 4,5-diselenolato-1,3-dithiole-2-thione (dsit) was prepared by the reaction of 1,3-dithiole-2-thione with in-situ generated lithium diisopropylamide and finely powdered elemental selenium. Addition of methanolic-ammoniacal solutions of the appropriate metal (nickel and palladium) dichlorides to the above reaction mixture followed by methanolic solutions of tetraalkylammonium (tetrabutylammonium (TBA) and tertraethylammonium (TEA)) bromide, results in the precipitation of dark colored solids from the solutions. Isolation and purification of these solids revealed that the solids had the general composition (TAA) sub 2 (M(dist)(sub 2)) where TAA were tetrabutylammonium or tetraethylammonium anions and M were Ni(II) and Pd(II). Electrochemical or chemical oxidation of the nickel(II) organometallic complexes resulted in the formation of the pi -acceptor (TBA) (Ni(dsit(sub 2))) while a similar reaction with the palladium(II) complexes failed to produce the equivalent (TAA) (Pd(dsit) (sub 2)). 12 refs., 1 tab. (ERA citation 13:040522)