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Author Kidder, Michelle ♦ Chaffe, Alan ♦ Nguyen, M. ♦ Buchanan, A. C. III
Sponsorship USDOE Office of Science (SC)
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Publisher American Chemical Society
Language English
Abstract There has been expanding interest in exploring porous metal oxides as a confining environment for organic molecules resulting in altered chemical and physical properties including chemical transformations. In this paper, we examine the pyrolysis behavior of phenethyl phenyl ether (PPE) confined in mesoporous silica by covalent tethers to the pore walls as a function of tether density and the presence of co-tethered surface spacer molecules of varying structure (biphenyl, naphthyl, octyl, and hexadecyl). The PPE pyrolysis product selectivity, which is determined by two competitive free-radical pathways cycling through the two aliphatic radical intermediates (PhCH CH2OPh and PhCH2CH OPh), is shown to be dramatically different from that measured in the liquid phase as well as for PPE tethered to the exterior surface of nonporous silica nanoparticles. Tailoring the pore surface with spacer molecules further alters the selectivity such that the PPE reaction channel involving a molecular rearrangement (O-C phenyl shift in PhCH2CH OPh), which accounts for 25 % of the products in the liquid phase, can be virtually eliminated under pore confinement conditions. The origin of this change in selectivity is discussed in the context of steric constraints on the rearrangement path, confinement effects, pore surface curvature, and hydrogen bonding of PPE with residual surface silanols supplemented by nitrogen physisorption data and molecular dynamics simulations.
ISSN 00223263
Educational Use Research
Learning Resource Type Article
Publisher Date 2011-01-01
Publisher Place United States
Journal Journal of Organic Chemistry
Volume Number 76
Issue Number 15
Organization Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)


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