Synthesis and some reactions of (α-tert-butyldioxyethoxy) diethylthallium

Russian Chemical Bulletin -     

Reaction of alkoxyl organomercury compounds with chloroform

Conclusions Derivatives of trichloromethylmercury RHgCCl₃ (R=n-C₃H₇, cyclo-C₆H₁₁, C₆H₅CH₂, and C₆H₅), which are stable in the absence of air, were obtained in almost quantitative yield by the reaction of the corresponding mercury tert-butoxides RHgOC(CH₃)₃ with chloroform at room temperature.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2803–2805, December, 1968.     

Thermal Decomposition of bis(cyclopentadienyl)hafnium compounds and their deuterated analogues

Thermal decomposition ranges of Cp₂HfR_, (R = Me, Ph) have been found by the DTA method. The thermal stability of hafnium derivatives greatly exceeds the stability of analogous titanium and zirconium compounds. Decomposition of Cp₂HfR₂ occurs by abstraction of σ-bonded groups which convert into RH. Hydrogen donors for the RH formation are both π-cyclopentadienyl and σ-bonded groups. The initial π-Cp₂Hf structure rearranges to form the (η⁵-Cp)-(η⁵,η¹-C₅H₄)Hf fragment. These react with HCl to produce Cp₂HfCl₂. It has been established that hydrogen exchange between cyclopentadienyl rings and methyl groups occurs during the thermal decomposition of Cp₂HfMe₂. As a result of the exchange process on thermal decomposition of Cp₂HfMe₂-d6, deuterium insertion into the cyclopentadienyl ring has been shown. The participation of solvent during the decomposition process of the hafnium derivatives has been studied.