Comp Chem Research Developments

October 4, 2000
 

IR Stretching Frequencies

In a paper appearing in J. Am. Chem. Soc. 122 (2000) 8271, graduate student Michael Sullivan and Professor Christopher Cramer, in collaboration with the experimental groups of Professor John Toscano of the Johns Hopkins University and Professor Dan Falvey of the University of Maryland, characterized key infrared stretching frequencies of matrix-isolated para-substituted phenylnitrenium ions. The theoretical calculations of the Minnesota group helped to establish that these species, which are potent human carcinogens, are better described as 4-iminocyclohexa-2,5-dienyl cations (i.e., they have quinoidal character) than as nitrenium ions. This characterization has important ramifications for the reactivity of these species in vivo and may help to guide future efforts in rational drug design.

 

Quinoidal stretching frequency of p-chlorophenylnitrenium computed with density functional theory.