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Title: The one-electron oxidation of an azazirconacyclobutene in the presence of B(C{sub 6}F{sub 5}){sub 3}

Abstract

Erker has used B(C{sub 6}F{sub 5}){sub 3} to generate active olefin polymerization catalysts by opening zirconacycles. In an effort to extend this work a heteroatom-substituted zirconacycle was treated with B(C{sub 6}F{sub 5}){sub 3}. The result is a partial oxidation to a radical cation. A typical {sup 1}H NMR of the heteroatom-substituted zirconacycle after the addition of B(C{sub 6}F{sub 5}){sub 3}. One set of phenyl resonances has broadened to the point of disappearance: The t-Bu signal has broadened substantially: the other phenyl resonances did not broaden significantly; the chemical shifts remain unchanged. Less broadening is observed when smaller amounts of B(C{sub 6}F{sub 5}){sub 3} are added. There is no immediate change in the {sup 19}F NMR of the B(C{sub 6}F{sub 5}){sub 3}. Such selective broadening has been seen in the {sup 1}H NMR spectrum of partially oxidized chlorophyll a and explained by electron exchange with the corresponding radical cation.

Authors:
; ; ;
Publication Date:
Research Org.:
Columbia Univ., New York (US)
Sponsoring Org.:
National Science Foundation (NSF); USDOE
OSTI Identifier:
20000104
DOE Contract Number:  
AC02-98CH10886
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 121; Journal Issue: 31; Other Information: PBD: 11 Aug 1999; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; ZIRCONIUM; HETEROCYCLIC COMPOUNDS; BORON COMPOUNDS; AROMATICS; FLUORINE; OXIDATION; CYCLOALKENES; ELECTRON EXCHANGE

Citation Formats

Harlan, C.J., Hascal, T., Fujita, E., and Norton, J.R. The one-electron oxidation of an azazirconacyclobutene in the presence of B(C{sub 6}F{sub 5}){sub 3}. United States: N. p., 1999. Web. doi:10.1021/ja984290j.
Harlan, C.J., Hascal, T., Fujita, E., & Norton, J.R. The one-electron oxidation of an azazirconacyclobutene in the presence of B(C{sub 6}F{sub 5}){sub 3}. United States. doi:10.1021/ja984290j.
Harlan, C.J., Hascal, T., Fujita, E., and Norton, J.R. Wed . "The one-electron oxidation of an azazirconacyclobutene in the presence of B(C{sub 6}F{sub 5}){sub 3}". United States. doi:10.1021/ja984290j.
@article{osti_20000104,
title = {The one-electron oxidation of an azazirconacyclobutene in the presence of B(C{sub 6}F{sub 5}){sub 3}},
author = {Harlan, C.J. and Hascal, T. and Fujita, E. and Norton, J.R.},
abstractNote = {Erker has used B(C{sub 6}F{sub 5}){sub 3} to generate active olefin polymerization catalysts by opening zirconacycles. In an effort to extend this work a heteroatom-substituted zirconacycle was treated with B(C{sub 6}F{sub 5}){sub 3}. The result is a partial oxidation to a radical cation. A typical {sup 1}H NMR of the heteroatom-substituted zirconacycle after the addition of B(C{sub 6}F{sub 5}){sub 3}. One set of phenyl resonances has broadened to the point of disappearance: The t-Bu signal has broadened substantially: the other phenyl resonances did not broaden significantly; the chemical shifts remain unchanged. Less broadening is observed when smaller amounts of B(C{sub 6}F{sub 5}){sub 3} are added. There is no immediate change in the {sup 19}F NMR of the B(C{sub 6}F{sub 5}){sub 3}. Such selective broadening has been seen in the {sup 1}H NMR spectrum of partially oxidized chlorophyll a and explained by electron exchange with the corresponding radical cation.},
doi = {10.1021/ja984290j},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 31,
volume = 121,
place = {United States},
year = {1999},
month = {8}
}