Detection and Characterization of a Transient Zwitterion, the 9-Carboxylate-9-fluorenyl Cation, and Its Conjugate Acid1

• Published in: Journal of the American Chemical Society Vol. 118; no. 48; pp. 12066 - 12073
• Main Authors: Lew, C. S. Q, Wagner, B. D, Angelini, Mark P, Lee-Ruff, E, Lusztyk, J, Johnston, L. J
• Format: Journal Article
• Language: English
• Published: American Chemical Society 04.12.1996
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja962066t

Laser flash photolysis of 9-hydroxy-9-fluorenecarboxylic acid in hexafluoro-2-propanol (HFIP) generates a transient with λmax at 495 nm that reacts with nucleophiles such as methanol and bromide and is insensitive to oxygen. In the presence of 0.15 M trifluoroacetic acid, a different transient with λmax at 560 nm that also reacts with nucleophiles is formed. The 495 and 560 nm species are identified as a zwitterion (the 9-carboxylate-9-fluorenyl cation) and its conjugate acid (the 9-carboxy-9-fluorenyl cation), respectively. The assignment of the zwitterion is supported by the observation of infrared absorptions in the carboxylate region that are quenched by nucleophiles with rate constants similar to those obtained by UV−visible detection. Both the zwitterion and its protonated form are observed at intermediate acid concentrations, leading to an estimate of 1 × 10-2 M-1 for the equilibrium constant for the ionization of the 9-carboxy-9-fluorenyl cation in HFIP. Absolute rate constants for reaction of the zwitterion with alcohols, anionic nucleophiles, and substituted aromatics are reported and compared to data for other 9-fluorenyl cations.