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Solvation and complexation of carbenes – a perspective
Author(s) -
Moss Robert A.
Publication year - 2011
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1869
Subject(s) - chemistry , dichlorocarbene , carbene , dibenzofuran , anisole , aryl , solvation , flash photolysis , photochemistry , computational chemistry , spectroscopy , medicinal chemistry , organic chemistry , ion , catalysis , kinetics , alkyl , physics , quantum mechanics , reaction rate constant
Complexes of several carbenes with aryl ethers are documented by laser flash photolysis with UV‐visible spectroscopic detection. The carbenes include methylchlorocarbene, benzylchlorocarbene, phenylchlorocarbene, p ‐nitrophenylchlorocarbene, and dichlorocarbene, whereas the complexing ligands are anisole, various methylanisoles, dibenzo‐18‐crown‐6, dibenzofuran, 1,3‐dimethoxybenzene, and 1,3,5‐trimethoxybenzene. The carbene complexes are characterized both by spectroscopy and computation. Complexation retards the additions of the carbenes to olefins. The complexation of phenylchlorocarbene by 1,3,5‐trimethoxybenzene is shown to be an equilibrium process, and the pertinent thermodynamic parameters are obtained by experiment and computed from theory. Copyright © 2011 John Wiley & Sons, Ltd.