Effect of phenyl substitution on the lifetime and product distribution of cyclobutylidene: preference change in the rearrangements via 1,2-carbon shift and 1,2-hydrogen shift

Steady state and laser flash photolytic experiments with precursors 6 and 11 revealed that diphenyl substitution affects the lifetime and reaction mode of cyclobutylidene. 2,2-Diphenylcyclobutylidene 3 (τ <0.1 ns) produces methylenecyclopropane 1 via 1,2-carbon in significant preference to the positional isomer 2 or cyclobutene 4. On the other hand, 3,3-diphenylcyclobutylidene 5 (τ = ca. 4 ns) gives 1,2-hydrogen shift product 4 more favorably than 1,2-carbon shift product 2 together with formal carbene dimer 14. MRMP2//MP2 calculations afford useful results to understand the interrelationship among substitution, structure, and reactivity.