화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.134, No.42, 17757-17768, 2012
Catalytic Trimerization of Bis-silylated Diazomethane
(Me3Si)(2)CNN isomerizes upon addition of traces of [Me3Si](+) ions to give (Me3Si)(2)NNC, which then undergoes an unusual trimerization reaction to give exclusively 4-diazenyl-3-hydrazinylpyrazole. As catalyst the isonitrilium ion, [(Me3Si)(2)NNC-(SiMe3)](+), was identified and fully characterized. Experiments and computations indicate a three-step reaction including isomerization of diazomethane, a C-C or N-C coupling, and a formal cycloaddition reaction. The kinetics and thermodynamics are discussed on the basis of DFT calculations.