The role of substituents on the addition of muonium to aromatics: As seen through muonium-radicals in allyl benzene compared to styrene,and from hammett parameters in aqueous solution |
| |
Authors: | J M Stadlbauer B W Ng D C Walker |
| |
Institution: | (1) Department of Chemistry and TRIUMF, University of British Columbia, V6T 1Y6 Vancouver, B.C., Canada;(2) Present address: Department of Chemistry, Hood College, 21701 Frederick, MD, USA;(3) Present address: Physical Sciences Division, Scarborough College, University of Toronto, M1C 1A4 Scarborough, Canada |
| |
Abstract: | Muonium-radicals resulting from insertion into the benzene ring are found to be much more prevalent in allyl benzene (C6H5CH2CH=CH2) than in styrene (C6H5CH=CH2). The salient implication of this comparison is that intramolecular rearrangements preceeded the μSR observation for the
case of styrene. In turn, this suggests that muonium-containing free radicals, as seen directly by kilogauss transverse field
μSR, are not necessarily theprimary radicals. Therefore, the elucidation of mechanism (and identification of the precursor) of Mu-radical formation is further
complicated by the fact that the observations may refer to thermodynamically more stable secondary radicals-those resulting
from a variety of intra-or inter-molecular relaxations or exchanges. Primary kinetic selectivities of thermalized muonium
atom addition reactions can be determined, however, through the substituent effect on the Hammett linear free energy parameter
in dilute solution. Results have been obtained for substituted benzenes and benzoic acids. Muonium apparently has a mild nucleophilic
character. And, most interestingly, this is opposite to that of its heavy isotope hydrogen. |
| |
Keywords: | |
本文献已被 SpringerLink 等数据库收录! |
|