Solid-State Chemistry, Kinetics, and Electron Spin Resonance Spectroscopy of 2-Biphenylmethylene

Article abstract of DOI:10.1021/jo00155a007

The chemistry and kinetics of 2-biphenylmethylene have been examined in low-temperature glasses and polycrystals.Photolysis of 2-biphenyldiazomethane at 77 K produces a single set of triplet carbene resonance peaks.They have been assigned to the unresolved superposition of syn and anti rotamers of the carbene.The carbene kinetics are fastest in diethyl ether glass.The decay rates of 4T in diethyl-d₁₀ ether and in a perfluorinated alkane polycrystal are comparable.This indicated that the main carbene reaction in diethyl ether is hydrogen atom abstraction.The reaction of 4T in diethyl-d₁₀ ether is a mixture of reaction with solvent and cyclization to fluorene.These interpretations are consistent with the observed product distributions.Matrix effects on the observed chemistry are discussed.