Cyclotrimerization of Acetylene in Gas Phase V(CH) Complexes: Detection of Intermediates and Products with Infrared Spectroscopy.

Infrared laser spectroscopy and mass spectrometry were used to determine the structures of intermediates and products in the single-atom-catalyzed trimerization of acetylene to form benzene. Complexes of the form V(CH) were produced in the gas phase via laser ablation in a pulsed-nozzle source, size-selected with a mass spectrometer, and studied with infrared laser photodissociation spectroscopy. Density functional theory calculations were performed in support of the experiments. Single- and double-acetylene complexes form V(CH) metallacycle structures. Three-acetylene complexes exhibit a surprising dependence on the acetylene concentration, forming V(CH) and (CH)V(CH) tri- and dimetallacycle ion structures at low concentrations and eventually V(benzene) at higher concentrations. These observations reveal intermediates along the reaction path of acetylene cyclotrimerization to benzene.