Spin trapping by nitrosoalkanes
Mechanisms of Some Photochemically Induced Reactions
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This thesis is based on the excellent radical scavenging properties of mono meric nitrosoalkanes RNO. Thus, addition of a small amount of RNO to a reacting system in which unstable radicals X· are generated usually results in the formation of relatively stable nitroxides, which can be studied by ESR spectroscopy at room temperature . . R-N=O + X --R-N-X ,. o The nature of the trapped radical X· can very often be deduced from the hyperfine splittings (hfs) and g-value of the ESR spectrum of the derived nitroxide. Thus the ESR Spin Trapping technique is useful for the identifi cation of highly...
This thesis is based on the excellent radical scavenging properties of mono meric nitrosoalkanes RNO. Thus, addition of a small amount of RNO to a reacting system in which unstable radicals X· are generated usually results in the formation of relatively stable nitroxides, which can be studied by ESR spectroscopy at room temperature . . R-N=O + X --R-N-X ,. o The nature of the trapped radical X· can very often be deduced from the hyperfine splittings (hfs) and g-value of the ESR spectrum of the derived nitroxide. Thus the ESR Spin Trapping technique is useful for the identifi cation of highly reactive (short-living) radicals X·. Chapter 1 contains a survey of the literature and a short description of the most important features of nitrosoalkanes, nitroxides and the Spin Trapping technique in general. In chapter 2 the synthesis of hitherto unknown I-nitrosoadamantane is described. Together with a number of other nitrosoalkanes it is used as a scavenger for trifluoromethyl radicals,generated by photolysis of trifluoro iodomethane. The derived alkyl trifluoromethyl nitroxides with aN = aF = 11.5-12.0 gauss are easily identified and are found to be very stable at room temperature. Chapter 3 illustrates the limitations of the Spin Trapping technique, i.e.
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