Photoelectron Spectroscopic Characterization of Methylated p-Block Radicals

This work has provided a systematic and comparative investigation of lowvalent main group radicals of the form E-CH3, spanning Groups 13, 15, and 16 of the periodic table. Through the combination of threshold photoelectron spectroscopy with mass-selective detection and pyrolytic precursor fragmentation, it was possible to isolate and characterize a wide range of transient species, many of which had not previously been observed in the gas phase. Notably, the ability to directly distinguish between σ- and π-bonding type structures, as well as to detect small changes in geometry upon ionization, highlights the power of ms-TPES for structural identification of reactive intermediates. The observed similarities and differences within and across groups offer insight not only into the underlying electronic structure of these species, but also into the broader reactivity landscape of low-valent main group chemistry.