Quantitative Aspects of Gas-Phase Metal Ion Chemistry: Conservation of Spin, Participation of f Orbitals, and C-H Activation and C-C Coupling.

In this Featured Article, I reflect on over 40 years of guided ion beam tandem mass spectrometry (GIBMS) studies involving atomic metal cations and their clusters throughout the periodic table. Studies that have considered the role of spin conservation (or lack thereof) are a primary focus with a quantitative assessment of the effects examined. A need for state-specific studies of heavier elements is noted, as is a more quantitative assessment of spin-orbit interactions in reactivity. Because GIBMS experiments explicitly evaluate the kinetic energy dependence of reactions over a wide range, several interesting and unusual observations are highlighted. More detailed studies of such unusual reaction events would be welcome. Activation of C-H bonds and ensuing C-C coupling events are reviewed, with future work encouraged. Finally, studies of lanthanides and actinides are examined with an eye on understanding the role of f orbitals in the chemistry, both as participants (or not) in the bonding and as sources/sinks of electron density. This area seems to be ripe for more quantitative experiments.