The Elusive Phenylethynyl Radical and Its Cation: Synthesis, Electronic Structure, and Reactivity.

Alkynyl radicals and cations are crucial reactive intermediates in chemistry, but often evade direct detection. Herein, we report the direct observation of the phenylethynyl radical (C6H5C 00000000000000000 00000000000000000 00000000000000000 01111111111111110 00000000000000000 01111111111111110 00000000000000000 01111111111111110 00000000000000000 00000000000000000 00000000000000000 C-center dot) and its cation (C6H5CC+), which are two of the most reactive intermediates in organic chemistry. The radical is generated via pyrolysis of (bromoethynyl)benzene at temperatures above 1500 K and is characterized by photoion mass-selected threshold photoelectron spectroscopy (ms-TPES). Photoionization of the phenylethynyl radical yields the phenylethynyl cation, which has never been synthesized due to its extreme electrophilicity. Vibrationally-resolved ms-TPES assisted by ab initio calculations unveiled the complex electronic structure of the phenylethynyl cation, which appears at an adiabatic ionization energy (AIE) of 8.90 +/- 0.05 eV and exhibits an uncommon triplet (3B1) ground state, while the closed-shell singlet (1A1) state lies just 2.8 kcal mol-1 (0.12 eV) higher in energy. The reactive phenylethynyl radical abstracts hydrogen to form ethynylbenzene (C6H5CCH) but also isomerizes via H-shift to the o-, m-, and p-ethynylphenyl isomers (C6H4CCH). These radicals are very reactive and undergo ring-opening followed by H-loss to form a mixture of C8H4 triynes, along with low yields of cyclic 3- and 4-ethynylbenzynes (C6H3CCH). At higher temperatures, dehydrogenation from the unbranched C8H4 triynes forms the linear tetraacetylene (C8H2), an astrochemically relevant polyyne. The reactive phenylethynyl radical, a key to PAHs in the ISM, was detected and spectroscopically characterized along with its singlet and triplet cations, and thermal products revealing a complex puzzle containing C8H5, C8H4, and C8H2 species.