title: A duality of mechanisms for the fragmentation of substituted benzyloxychlorocarbenes.
abstract: Substituted benzyloxychlorocarbenes (X-PhCH2OCCl) were generated photochemically at 25 degrees C in dichloroethane from appropriate diazirine precursors. Fragmentations of the carbenes produced were determined by laser flash photolysis. The data (X, kfrag in s-1) were: p-Me, 2.6 x 105; p-Ph, 8.3 x 104; H, 6.0 x 104; p-Cl, 5.2 x 104; m-Cl, 1.3 x 105; p-F3C, 2.1 x 106; p-O2N, 6.3 x 106. A Hammett correlation of log kfrag versus sigma+ was parabolic. The curvature was taken to imply the gradual change of the fragmentation mechanism from predominantly heterolytic for X-PhCH2CCl with electron-donating X (with developing positive charge on the benzylic carbon in the transition state) to predominantly homolytic for carbenes with electron-withdrawing X. This idea was supported by computational studies.
authors.affiliation: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, NJ 08903, USA. moss@rutchem.rutgers.edu
authors.forename: Robert A
authors.initials: RA
authors.lastname: Moss
authors.forename: Yan
authors.initials: Y
authors.lastname: Ma
authors.forename: Ronald R
authors.initials: RR
authors.lastname: Sauers