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45, 385 (1949). M. S. Kharasch, A, C. Poshkus, A. , 16, 1458 (1951). (1950). J. W. Nudenberg, /. Org. DIRADICALS 49 However, the diradicals formed by the photolysis of 1,4,5-oxadithiacycloheptane in methyl methacrylate add at most a few monomer units before the chain is is 92 stopped by ring closure. One of the possible mechanisms of cis-trans isomerization of olefins ' excitation to the triplet or diradical state. 93 95 The two paths, one by way of singlet states, are and triplet states diagrammed in Fig.

It is unknown whether of both the radical-like reactions some compounds are characteristic of their singlet states directly or due to an undetectable amount of a more reactive triplet state in of equilibrium. Stable Diradicals The most fact that its two familiar diradical uppermost is the oxygen molecule. occupied orbital orbitals of equal energy, the last Due degenerate and to the consists of two electrons each occupy one of these and the ground state is a diradical. 39 is A recently developed analytical CHAPTER 40 method III oxygen depends on its paramagnetism.

Since the uptake of oxygen obeys the same kinetic law, it is a reasonable extrapolation to suppose that here too the rate-determining step is a dissociation into radicals. When one of the phenyl groups in triphenylmethyl is replaced by a cyclohexyl group, the rate of dissociation of the ethane is reduced by a factor of 170. 38 Some dissociation A rate parameters are given in Tables III and B. When solutions of ethanes with four aryl groups K. , 551, 127 (1942). 4 symmetrical tetraphenyl-1,2dialkylethanes a K.

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