Mass spectrometry with flash photolysis

Organic stractures can be determined accurately and quickly by spectroscopic methods. Mass spectrometry determines mass of a molecule and its atomic composition. NMR spectroscopy reveals the carbon skeleton of the molecule, whereas IR spectroscopy determines functional groups in the molecules. UV-visible spectroscopy tells us about the conjugation present in a molecule. Spectroscopic methods have also provided valuable evidence for the intermediacy of transient species. Most of the common spectroscopic techniques are not appropriate for examining reactive intermediates. The exceptions are visible and ultraviolet spectroscopy, whose inherent sensitivity allows them to be used to detect very low concentrations for example, particularly where combined with flash photolysis when high concentrations of the intermediate can be built up for UV detection, or by using matrix isolation techniques when species such as ortho-benzyne can be detected and their IR spectra obtained. Unfortunately, UV and visible spectroscopy do not provide the rich structural detail afforded by IR and especially H and NMR spectroscopy. Current mechanistic studies use mostly stable isotopes such as H, and 0. Their presence and position in a molecule can... 

Carbocations are intermediates in several kinds of reactions. The more stable ones have been prepared in solution and in some cases even as solid salts, and X-ray crystallographic structures have been obtained in some cases. An isolable dioxa-stabilized pentadienylium ion was isolated and its structure was determined by h, C NMR, mass spectrometry (MS), and IR. A P-fluoro substituted 4-methoxy-phenethyl cation has been observed directly by laser flash photolysis. In solution, the carbocation may be free (this is more likely in polar solvents, in which it is solvated) or it may exist as an ion pair, which means that it is closely associated with a negative ion, called a counterion or gegenion. Ion pairs are more likely in nonpolar solvents. 

Analysis of the products of the photolysis of Zr (benzyl) 4 in toluene at 30°C in the region 300-450-nm with mass spectrometry shows that the predominant peak is due to p-benzyl toluene with small amounts of dibenzyl, and 4,4 -dimethyl diphenyl. Rate measurements (Fig. 5a) suggest that in this region of the spectrum the polymerization proceeds through radical intermediates (29). This concept is supported by the fact that the spectrum of zirconium tetrabenzyl has a maximum at 317 nm and is identical with that found for the benzyl radical using flash photolysis techniques (30). Also zirconium tetrabenzyl on irradiation in toluene solution produces... 

Flash Photolysis with Time-Resolved Mass Spectrometry (Carr). 

FLASH PHOTOLYSIS WITH TIME-RESOLVED MASS SPECTROMETRY... 

Figure 1. Schematic diagram of instrumentation for flash photolysis with time-resolved mass spectrometry.

Flash Photolysis With Time-Resolved Mass Spectrometry 1... 

Electron impact mass spectrometry of the cyclobutanedione (24) gives rise to dimethylcarbene radical cation.35 Appearance energy measurements and ah initio calculations indicated that the radical cation lies 84 kJ mol 1 above the propene radical cation and is separated from it by a barrier of 35 kJ mol-1. Diarylcarbene radical cations have been generated by double flash photolysis of diaryldiazomethanes in the presence of a quinolinium salt (by photo-induced electron transfer followed by photo-initiated loss of N2).36 Absolute rate constants for reactions with alkenes showed the radicals to be highly electrophilic. In contrast to many other cation radicals, they also showed significant radicophihc properties. 

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