Abstract
The /sup 60/Co gamma radiolysis of cyclohexane solutions of o- carborane and 1-ethyl-, 1-vinyl-, and 1-allyl-o-carborane was studied for solute concentration in the range 0.5-200 mM. The value of G(H/sub 2/) decreases with increase in solute concentration and values of the ion scavenging coefficient alpha of 33 M/sup -1/ for o-carborane and 1-ethyl-o-carborane and 10.6 M/sup -1/ for 1-vinyl- and 1-allyl-ocarborane were calculated, suggesting efficient electron scavenging by these solutes. Lower limits for the ratio of the specific rate of hydrogen abstraction from cyclohexane to the specific rate of addition to 1-alkenyl-o-carboranes is estimated for the hydrogen atom to be 0.0031 for 1- vinyl-o-carborane and 0.002 for 1-allyl-o-carborane. Yields of cyclohexene, dicyclohexyl, and cyclohexyl addition products with the 1-allcenyl-o-carboranes are consistent with electron and radical scavenging. The ultraviolet absorption spectra of the o-carboranes is discussed and the possibility of energy transfer from electronically excited cyclohexane to the o-carborane solutes is suggested. The results are related to previous studies of radiation-induced addition polymerization of 1-alkenyl-o-carboranes. (auth)
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