Electronic Structure and Excited-State Dynamics of an Arduengo-Type Carbene and its Imidazolone Oxidation Product

We describe an investigation of the excited-state dynamics of isolated 1,3-di-tert-butyl-imidazoline-2-ylidene (tBu₂ Im, C₁₁ H₂₀ N₂ , m/z=180), an Arduengo-type carbene, by time- and frequency-resolved photoionization using a picosecond laser system. The energies of several singlet and triplet excited states were calculated by time-dependent density functional theory (TD-DFT). The S₁ state of the carbene deactivates on a 100 ps time scale possibly by intersystem crossing. In the experiments we observed an additional signal at m/z=196, that was assigned to the oxidation product 1,3-di-tert-butyl-imidazolone, tBu₂ ImO. It shows a well-resolved resonance-enhanced multiphoton ionization (REMPI) spectrum with an origin located at 36951 cm^-1 . Several low-lying vibrational bands could be assigned, with a lifetime that depends strongly on the excitation energy. At the origin the lifetime is longer than 3 ns, but drops to 49 ps at higher excess energies. To confirm formation of the imidazolone we also performed experiments on benzimidazolone (BzImO) for comparison. Apart from a redshift for BzImO the spectra of the two compounds are very similar. The TD-DFT values display a very good agreement with the experimental data.