Phenyl derivatives of organotitanium compounds

Abstract

Thermally unstable tetraphenyltitanium has been obtained by the interaction of 4 moles of phenyllithium with titanium tetrachloride in benzene solution at −70°. It reacts with mercuric chloride at the same temperature with quantitative formation of phenylmercury chloride. In ether-cyclopentadiene solution, because of the replacement of two phenyl groups, dicyclopentadienyldiphenyltitanium is formed. At −10° tetraphenyltitanium decomposes, 1 mole of biphenyl is formed, and black pyrophoric diphenyltitanium, stable at room temperature and in an inert atmosphere, has been isolated. The oxidation of diphenyltitanium in benzene labelled with 14C shows that both products of the oxidation, phenol and biphenyl, do not contain the label. A chloroform solution of diphenyltitanium decomposes at room temperature with the formation of benzene, titanium tetrachloride and biphenyl. A black crystalline precipitate of diphenyltitanium ammine has been obtained by the action of ammonia on a solution of diphenyltitanium in benzene. It is easily oxidised in air. Only about 40% of the theoretical yield of phenylmercury chloride is obtained by the action of mercuric chloride on a solution of diphenyltitanium in either. Phenylmercury chloride reacts with the organotitanium compound with formation of benzene, metallic mercury, calomel and ethylmercury derivatives. The formation of ethylmercury chloride was the result of a homolytical procedure with the solvent, diethyl ether.