Reversible O-Ylide Formation in Carbene/Ether Reactions

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Abstract
p-Nitrophenylchlorocarbene reacted reversibly with diethyl ether, di-n-propyl ether, or tetrahydrofuran (THF) to form O-ylides, which were visualized by their UV–visible spectroscopic signatures. Equilibrium constants (Keq) were determined spectroscopically and ranged from 0.10 M–1 (di-n-propyl ether) to 7.5 M–1 (THF) at 295 K. Studies of Keq as a function of temperature afforded ΔHo, ΔSo, and ΔGo for the di-n-propyl ether and THF/O-ylide equilibria. ΔHo was favorable for ylide formation, but ΔSo was quite negative, so that ΔGos for the equilibria were small. Electronic structure calculations based on density functional theory provided structures, spectroscopic signatures, and energetics for the carbene/ether O-ylides.

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