Structure of the intermediate formed in the reaction of the styrene radical cation and neutral styrene

Abstract

emphasized that our estimation of isocyanide isomerization energies does not require knowledge of any heats of formation.The core binding energies of tert-butyl isocyanide, tert-butyl cyanide,33 phenyl isocyanide, and benzonitrile33 can be used to predict values for the corresponding isocyanide-to-cyanide isomerization enthalpies. The isomerization enthalpy is calculated to be -27 kcal mol"1 for Zcrf-butyl isocyanide and -28 kcal mol"1 for phenyl isocyanide. Given the uncertainty in the core replacement energies (~5 kcal mol"1), our results indicate that A£lso (33) To be consistent with our assignment of the CH3CN spectrum, we assume that the carbon Is binding energy of the CN carbon atom of a nitrile is always lower than that of the carbon atom directly bonded to the CN group. Thus we take 291.8 and 291.85 eV for the CN carbon atoms of (CH3)3CN23 and C6H5CN,34 respectively.for the isocyanide RNC is essentially independent of the R group.

Use of electrospray ionization mass spectrometry for the investigation of radical cation chain reactions in solution: detection of transient radical cations

“…6a) of 3 has a very weak parent ion at m/z 296. The base peak m/z 148 is formed by cycloreversion of the cyclobutane ring [24]. Surprisingly, the high-energy CID spectrum (Fig.…”

Electron-Transfer-Catalyzed Dimerization oftrans-Anethole: Detection of the Distonic Tetramethylene Radical Cation Intermediate by Extractive Electrospray Ionization Mass Spectrometry

“…This ion is expected formed by a typical radical-initiated fragmentation. [12][13][14] In contrast, with longer reaction times of, for instance, 16 s the intensity of this fragment ion was reduced to <5%. The spectrum (Figure 1b) shows almost exclusively ion 3 c…”

Bicyclobutonium ion versus cyclopropylcarbinyl cation chemistry: the cycloaddition reaction with ethene in the dilute gas phase

“…The pressure of the CS 2 bath gas was used to modulate the internal energy of the ions via collisional cooling. [27][28][29][30][31] All chemicals were obtained from Aldrich Chemical (Milwaukee, WI, USA) and used without further purification.…”

“…Changes in the structure or composition of analyte ions that originate from the various precursors were probed by using tandem mass spectrometry, where the ion structure was evaluated as a function of internal energy by an established technique. [27][28][29][30][31] Via this technique, the internal energy was varied by generating the analyte cations within a high-pressure, chemical ionization source in the presence of an inert bath gas. The bath gas, CS 2 , which also served as a charge exchange gas, collisonally stabilized the analyte ion of interest once formed.…”