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Author Maxey, C. T. ♦ Sleiman, H. F. ♦ Massey, S. T.
Sponsorship USDOE
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword CHEMISTRY ♦ TUNGSTEN COMPLEXES ♦ CHEMICAL REACTIONS ♦ ORGANIC NITROGEN COMPOUNDS ♦ CARBONYLS ♦ ELECTRONIC STRUCTURE ♦ CARBENES ♦ REACTION INTERMEDIATES
Abstract The reaction of cis-azobenzene with a series of para substituted phenyl carbenes (CO){sub 5}W=C(OMe)P-XC{sub 6}H{sub 4} (X = H, OMe, CF{sub 3}) was carried out in both noncoordinating and coordinating solvents. The stability and reactivity of the initially formed zwitterionic species (CO){sub 5} WNPhNPhC(OMe)(p-XC{sub 6}H{sub 4}) depended on the substituent X. In noncoordinating solvents, the unsubstituted zwitterionic species (CO){sub 5}WNPhNPhC(OMe)C{sub 6}H{sub 5} was converted into an isomeric zwitterionic intermediate and a 2,4-diazametallacycle. Both isomeric zwitterions and the 2,4-diazametallacycle formation was shown to involve the intermediacy of a coordinated diaziridine in which the metal subsequently inserts into the N-N bond. When the unsubstituted zwitterion was decomposed in CH{sub 3}CN, the coordinated diaziridine was displaced by solvent, inhibiting formation of the 2,4-diazametallacycle. 34 refs., 6 figs., 2 tabs.
ISSN 00027863
Educational Use Research
Learning Resource Type Article
Publisher Date 1992-06-17
Publisher Place United States
Journal Journal of the American Chemical Society
Volume Number 114
Issue Number 13


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