102146-13-4Relevant articles and documents
O -ylide and π-complex formation in reactions of a carbene with dibenzo and monobenzo crown ethers
Hoijemberg, Pablo A.,Moss, Robert A.,Feinblum, David V.,Krogh-Jespersen, Karsten
, p. 6230 - 6238 (2014)
Reactions of p-nitrophenylchlorocarbene (PNPCC) with various dibenzo crown ethers produce O-ylides and π-complexes; the reactions can be followed via the spectral signatures of the carbene and the products. The O-ylides form most rapidly, but over time th
Reversible O -ylide formation in carbene/ether reactions
Hoijemberg, Pablo A.,Moss, Robert A.,Krogh-Jespersen, Karsten
experimental part, p. 358 - 363 (2012/03/12)
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.
Hammett studies of aryldichloromethide carbanion reactions
Moss, Robert A.,Tian, Jingzhi
, p. 1245 - 1247 (2007/10/03)
Rate constants were measured for the capture of para-substituted phenylchlorocarbenes by chloride ions to form aryldichloromethide carbanions and for the additions of these carbanions to acrylonitrile. Hammett analyses give ρ = +0.86 for the former reacti
