The Elusive Benzocyclobutenylidene:  A Combined Computational and Experimental Attempt

• Published in: Journal of the American Chemical Society 2001-03, Vol.123 (12), p.2870-2876
• Main Authors: Nicolaides, Athanassios, Matsushita, Takeshi, Yonezawa, Kohichi, Sawai, Shinji, Tomioka, Hideo, Stracener, Louise L, Hodges, Jonathan A, McMahon, Robert J
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja0039482

Ab initio and density functional theory calculations predict that benzocyclobutenylidene (1) has a singlet ground state in contrast to the parent phenylcarbene and many other simply substituted arylcarbenes. Calculations also predict that 1 should lie in a relatively deep potential well, while its triplet state is 14.5 kcal mol-1 higher in energy. However, attempts to observe 1 directly by photolysis of two different nitrogenous precursors were not successful. Irradiation of diazobenzocyclobutene (7) (λ > 534 nm or λ > 300 nm) or azibenzocyclobutene (10) (λ > 328 nm) in Ar matrixes at 10 K leads to the formation of the strained cycloalkyne 7-methylenecyclohepta-3,5-dien-1-yne (3). 13C-Labeled 3 was also prepared in a similar manner. There is very good agreement between experimental IR spectra and computationally derived harmonic vibrational frequencies for 3 and [13C]-3 and excellent agreement between observed and calculated isotopic shifts. Prolonged short-wavelength irradiation converts 3 into benzocyclobutadiene (5). Phenylacetylene (6) and benzocyclobutadiene dimer (11) were identified as products arising from flash vacuum pyrolysis of diazirine 10 at 500 °C.