Negative Ion Photoelectron Spectroscopy and Its Use in Investigating the Transition States for Some Organic Reactions

Abstract

Abstract This chapter describes the use of negative ion photoelectron spectroscopy (NIPES) for investigating the transition states (TSs) for several organic reactions: (a) ring inversion and bond shifting in cyclooctatetraene, (b) ring opening and ring closure of cyclopropanone via an oxyallyl TS, and (c) fragmentation of triplet cyclopropanetrione [(CO) 3 ] to CO plus triplet ethylenedione (O C C O). The application of NIPES to access the D 3h hilltop for fragmentation of singlet (CO) 3 to three molecules of CO is also described, and the use of NIPES for TS spectroscopy of X + HX ➔ XH + X reactions is discussed.