Electron transfer and bond-forming reactions following collisions of I2+ with CO and CS2

Collisions between I2+ and CO have been investigated using time-of-flight mass spectrometry at a range of centre-of-mass collision energies between 0.5 and 3.0 eV. Following I2++CO collisions, we detect I++CO+ from a single-electron transfer reaction and IO++C+ from bond-forming reactivity. Reaction-window calculations, based on Landau-Zener theory, have been used to rationalise the electron transfer reactivity and computational chemistry has been used to explore the [I-CO](2+) potential energy surface to account for the observation of IO+. In addition, collisions between I2+ and CS2 have been investigated over a range of centre-of-mass collision energies between 0.8 and 6.0 eV. Both single- and double-electron transfer reactions are observed in the I2+/CS2 collision system, an observation again rationalised by reaction-window theory. The monocations IS+ and IC+ are also detected following collisions of I2+ with CS2, and these ions are clearly products from a bond-forming reaction. We present a simple model based on the structure of the [I-CS2](2+) collision complex to rationalise the significantly larger yield of IS+ than IC+ in this bond-forming process.