Generation, characterization, and kinetics of triplet Di[1,2,3,4,5,6, 7,8-octahydro-1,4:5,8-di(ethano)anthryl]carbene

The title carbene has been generated by photolysis of the corresponding diazo precursors and studied by spectroscopic means, i. e., electron paramagnetic resonance (EPR) and UV/vis spectroscopy in matrixes at low temperature and laser-flash photolysis in solution at room temperature, with the product analysis. The results are compared with triplet di(2,3,5,6-tetramethylphenyl)carbene, an open-chain counterpart, which revealed that bicycloalkyl groups are acting as a fairly good kinetic protector for the triplet carbene as opposed to the open-chain counterpart. The formation of all-hydrocarbon triplet carbenes having a half-life over a second under normal conditions was realized for the first time. Effects of para-substituents on the structure and reactivities of the carbene are also investigated and discussed in terms of polar and spin electronic effects.