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

Tarun Roy; Venkatesan S Thimmakondu; Subhas Ghosal

doi:10.1021/acsomega.2c03224

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

ACS Omega. 2022 Aug 19;7(34):30149-30160. doi: 10.1021/acsomega.2c03224. eCollection 2022 Aug 30.

Authors

Tarun Roy¹, Venkatesan S Thimmakondu², Subhas Ghosal¹

Affiliations

¹ Department of Chemistry, National Institute of Technology Durgapur, M G Avenue, Durgapur 713 209, India.
² Department of Chemistry and Biochemistry, San Diego State University, San Diego, California 92182-1030, United States.

Abstract

1-Azulenylcarbene (18; 0 kJ mol^-1) 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 C₁₁H₈ elemental composition that either energetically lie below or very close to 18. While the cyclic allene, bicyclo[5.4.0]undeca-2,3,5,7,9,11-hexene (1; -166 kJ mol^-1), is the experimentally known lowest energy isomer, three other cyclic allenes, bicyclo[5.4.0]undeca-1,2,4,6,8,10-hexene (2; -100 kJ mol^-1), bicyclo[5.4.0]undeca-1,3,4,6,8,10-hexene (3; -97 kJ mol^-1), and bicyclo[6.3.0]undeca-1,2,4,6,8,10-hexene (13; -42 kJ mol^-1), demand new experimental studies. In total, thirty-one isomers are studied in this work (within -166 to +15 kJ mol^-1 from 18) and all are found to be polar (μ ≠ 0). Among these, 1H-benzo[7]annulen-1-ylidene (17; -4 kJ mol^-1; μ = 5.24 D), bicyclo[5.4.0]undeca-2,4,6,8,11-pentaene-10-ylidene (24; 13 kJ mol^-1; μ = 7.59 D), 5-methylene-naphthalen-1-ylidene (26; 15 kJ mol^-1; μ = 5.32 D), 6-methylene-naphthalen-2-ylidene (27; -43 kJ mol^-1; μ = 6.60 D), and 8-methylene-naphthalen-2-ylidene (28; -39 kJ mol^-1; μ = 5.55 D) are competitively polar compared to 18 (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.