Preparation and characterization of new organometallic compounds synthesized by using metal vapours

Abstract

A method to vapourize thorium metal, which had not been employed previously, was developed and the method of vapourizing zirconium metal was improved. Several new organometallic compounds were synthesized using the metal atom vapourization technique. The vapour reactions of thorium, zirconium and tungsten with several different ligands were examined. The structures of the new compounds were elucidated mainly from their 1H NMR, 13C NMR, IR and Mass spectra. Some of the products were investigated by elemental analysis and molecular weight determinations. The application of thorium vapour to organometallic synthesis proved disappointing. More fruitful investigations arose from the study of zirconium vapour. The first examples of metal vapour reactions leading to oxidative addition of zirconium atoms to carbon-hydrogen and carbon-carbon bonds of alkanes at cryogenic temperatures were presented. This kind of behaviour is uni q ue among the metal atoms studied up to this time. An investigation of an interesting organometallic compound derived from zirconium and pentamethylcyclopentadiene was carried out. Several previously unknown arene complexes of tungsten and zirconium as well as the first example of the novel zerovalent six-coordinate complex hexakis(diethylaminodifluorophosphine)tungsten were prepared. High vacuum and inert atmosphere methods were used for handling these air sensitive compounds.