The Solvation of Carbenes: π and O-Ylidic Complexes of p-Nitrophenylchlorocarbene
Authors:
- 24 April 2008
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry A
- Vol. 112 (20) , 4651-4659
Abstract
P-Nitrophenylchlorocarbene (PNPCC) was studied by laser flash photolysis with UV-vis detection in solution at ambient temperature. The π → p (316 nm) and σ → p (628 nm) absorptions of PNPCC were replaced in π- or O-donor solvents by absorptions due to π- or O-ylidic complexes or O-ylides. Donors included anisole, 1,3-dimethoxybenzene, 1,3,4,5-tetramethoxybenzene, diethyl ether, 18-crown-6, and dibenzo-18-crown-6. Suggestive evidence was also obtained for weak π-complexation of PNPCC by benzene. Computational studies aided in understanding the carbene complex and O-ylide absorption spectra, and they provided structures and energetics for these species.Keywords
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