New Carbenes and Cyclic Allenes Energetically Comparable to Experimentally Known 1-Azulenylcarbene.

1-Azulenylcarbene (; 0 kJ mol) is experimentally known as the key reactive intermediate for the rearrangement reactions of aryl carbenes in the laboratory. Here, using coupled-cluster methods up to the fc-CCSD(T)/cc-pVTZ//fc-CCSD(T)/cc-pVDZ level, thirteen new carbenes and one new cyclic allene are theoretically identified within the CH elemental composition that either energetically lie below or very close to . While the cyclic allene, bicyclo[5.4.0]undeca-2,3,5,7,9,11-hexene (; -166 kJ mol), is the experimentally known lowest energy isomer, three other cyclic allenes, bicyclo[5.4.0]undeca-1,2,4,6,8,10-hexene (; -100 kJ mol), bicyclo[5.4.0]undeca-1,3,4,6,8,10-hexene (; -97 kJ mol), and bicyclo[6.3.0]undeca-1,2,4,6,8,10-hexene (; -42 kJ mol), demand new experimental studies. In total, thirty-one isomers are studied in this work (within -166 to +15 kJ mol from ) and all are found to be polar (μ ≠ 0). Among these, 1H-benzo[7]annulen-1-ylidene (; -4 kJ mol; μ = 5.24 D), bicyclo[5.4.0]undeca-2,4,6,8,11-pentaene-10-ylidene (; 13 kJ mol; μ = 7.59 D), 5-methylene-naphthalen-1-ylidene (; 15 kJ mol; μ = 5.32 D), 6-methylene-naphthalen-2-ylidene (; -43 kJ mol; μ = 6.60 D), and 8-methylene-naphthalen-2-ylidene (; -39 kJ mol; μ = 5.55 D) are competitively polar compared to (μ = 5.39 D). Therefore, these carbene molecules are potential targets for rotational spectroscopists and radioastronomers. Considering the importance of naphthyl and azulenylcarbenes in reactive intermediate chemistry, mechanisms of different rearrangement reactions and plausible formation pathways of some of these new carbenes are studied in this work using density functional theory.