62850-21-9Relevant academic research and scientific papers
Computational and matrix isolation studies of tetra-tert-butylethane
Bucher, Goetz
, p. 4340 - 4345 (2009)
Irradiation of cryogenic xenon matrices containing the sterically congested alkane tetra-tert-butylethane (1) with intense pulses from a KrF excimer laser (λexc = 248 nm) have resulted in the formation of methane and isobutene as the major products. Larger fragments derived from 1, such as 2,2-dimethylbutane (10), were also detected, whereas no evidence was obtained for the formation of the elusive tetra-tert-butylethylene (2). The results suggest that biphotonic irradiation of xenon matrices containing tert-butylated precursor molecules may generally result in the efficient formation of isobutene and smaller alkanes. An analysis of the decomposition reactions of 1 by various computational methods revealed that commonly used DFT methods, such as B3LYP or BLYP, and MP2 theory do not provide a good description of the energetics of the decay reactions of the sterically overloaded alkane 1. The recently developed M05-2X method was the only method among those tested to yield an activation enthalpy for the cleavage of 1 in agreement with the experimental value.
Aliphatic Azo Compounds, XV cis- and trans-Tetracyclopropyl- and Tetra-tert-butylazomethanes
Bernloehr, Werner,Flamm-ter Meer, Manuela A.,Kaiser, Juergen H.,Schmittel, Michael,Beckhaus, Hans-Dieter,Ruechardt, Christoph
, p. 1911 - 1918 (2007/10/02)
The products and the kinetics of the thermolysis of the title compounds 3 and 5 were investigated.Like the trans-isomers, the cis-azo compounds also undergo homolytic decomposition without accompanying cis-trans-isomerization.The observed structure-reactivity relationships are discussed.On irradiation of trans-tetra-tert-butylazomethane (trans-5) at 60-120 deg C in benzene or chlorobenzene an almost quantitative yield of 1,1,2,2-tetra-tert-butylethane is obtained.
