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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}

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/ja984290j· OSTI ID:20000104

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.

Research Organization:
Columbia Univ., New York (US)
Sponsoring Organization:
National Science Foundation (NSF); USDOE
DOE Contract Number:
AC02-98CH10886
OSTI ID:
20000104
Journal Information:
Journal of the American Chemical Society, Vol. 121, Issue 31; Other Information: PBD: 11 Aug 1999; ISSN 0002-7863
Country of Publication:
United States
Language:
English