title: Fragmentation of 2,2,2-triphenylethoxychlorocarbene: evidence for ultrafast fragmentation-rearrangement in excited diazirines.
abstract: [reaction: see text] Photolysis of 3-(2,2,2-triphenylethoxy)-3-chlorodiazirine gives 2,2,2-triphenylethoxychlorocarbene which fragments with 1,2-phenyl migration and loss of CO and Cl(-) to yield the 1,1,2-triphenylethyl cation and thence 1,1,2-triphenylethene by proton loss. However, ps and fs laser flash photolysis provides evidence that up to 25% of the alkene product stems from carbocation that arises directly from excited diazirine rather than from the carbene.
authors.affiliation: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, USA.
authors.forename: Xiaolin
authors.initials: X
authors.lastname: Fu
authors.forename: Robert A
authors.initials: RA
authors.lastname: Moss
authors.forename: Piotr
authors.initials: P
authors.lastname: Piotrowiak
authors.forename: Mykhaylo
authors.initials: M
authors.lastname: Myahkostupov
authors.forename: Ian R
authors.initials: IR
authors.lastname: Gould