SOLID-STATE CHEMISTRY, KINETICS, AND SPECTROSCOPY OF 1,2-DIPHENYLPROPYLIDENE.

Article abstract of DOI:10.1021/ja00353a033

Photolysis of a diazo compound at low temperatures produces an intense ESR spectrum of a triplet carbene. The only kinetically important process of triplet carbene in glasses at low temperature is hydrogen atom abstraction from the matrix. Triplet carbene is long lived in polycrystals, and the products observed may be due in part to annealing a sample containing unreacted carbene. Studies of triplet carbene in perfluorinated matrices between -154 and -170 C. Revealed that 1,2 hydrogen atom shifts occur from the triplet by an unknown mechanism. Singlet carbene undergoes shifts without any appreciable product isotope effect. The chemistry and kinetics of both singlet and triplet in the solid state are strongly influenced by the matrix.