Adamantylidenecarbene: Photochemical Generation, Trapping, and Theoretical Studies

Photolysis of 1-(2-adamantylidene)-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene in benzene (or benzene-d₆) at ambient temperature produces adamantylidenecarbene. The carbene undergoes dimerization to a cumulene and may also be trapped in a stereospecific fashion by cis- and trans-4-methyl-2-pentene. No products attributable to 4-homoadamantyne, resulting from ring expansion of the carbene, could be detected. Coupled cluster/density functional theory calculations place the singlet carbene ∼49 kcal/mol below the triplet and show that the former must overcome a barrier of ∼13.5 kcal/mol to rearrange into 4-homoadamantyne.