On the formation of the isomeric cluster ions (CO)+n

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Abstract
The kinetics and equilibria of clustering reactions (CO)+n−1+CO=(CO)+n (n=3–18) were studied, using a pulsed electron‐beam high‐pressure mass spectrometer. It was found that there are two isomers for the tetramer (CO)+4. The energy barrier for the isomerization reaction was measured to be 6.1 kcal/mol. Anomalous van’t Hoff plots for the clustering reactions were obtained with n=8–10, probably due to the existence of several isomeric cluster ions. The structures of the cluster ions (CO)+n with n=2–5 were examined by ab initio MO calculations. Two core ions of n=3, σ and π radical cations, are found to give different clustering patterns.

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