Clark T (1995)
Publication Status: Published
Publication Type: Journal article
Publication year: 1995
Publisher: American Chemical Society
Book Volume: 14
Pages Range: 2570-2574
Journal Issue: 5
DOI: 10.1021/om00005a064
Irradiation of CdS powder suspended in ethereal solutions of organolithium compounds, RLi, yields elemental Cd and the photooxidation products R-R. The mechanism is shown to be a radical one, the products R-R at least partly resulting from intraaggregate dimerization of radicals R(.) if the parent RLi is aggregated. Free solution-phase radicals have not been detected. The configuration of a benzyl anion adsorbate has been investigated using AM1 semiempirical molecular orbital calculations on a ZnS model surface. These suggest that eta(1)- and eta(7)-bound species compete with each other. A comparison of the reactivity of PhCH(2)Li and two alkyl-substituted, sterically hindered derivatives shows that the substituted benzylic species, which are eta(1)-bound, react faster than PhCH(2)Li. We therefore propose that PhCH(2)Li prefers a eta(7) configuration on the active CdS surface.
APA:
Clark, T. (1995). INVESTIGATION OF ORGANOLITHIUM DIMERIZATION ON IRRADIATED CDS POWDER. Organometallics, 14(5), 2570-2574. https://dx.doi.org/10.1021/om00005a064
MLA:
Clark, Timothy. "INVESTIGATION OF ORGANOLITHIUM DIMERIZATION ON IRRADIATED CDS POWDER." Organometallics 14.5 (1995): 2570-2574.
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