title: Exploring the Gas Phase Synthesis of the Elusive Class of Boronyls and the Mechanism of Boronyl Radical Reactions under Single Collision Conditions.
abstract: Until recently, the chemistry of boronyl (BO), a diatomic radical isolectronic with the cyano (CN) species, has remained unknown. The boronyl group is characterized by a boron-oxygen multiple bond, and because of the inherent electron deficiency of the boron atom, boronyls (RBO) are highly reactive and typically only exist in their cyclotrimeric form (RBO)3. Due to their invaluable role as reactants, the isolation of the monomers in gas phase experiments has been extensively sought after by the organic synthesis and physical organic chemistry communities but never achieved. Besides the interests from a physical organic and synthetic point of view, boronyls also play a role as reaction intermediates in boron-assisted rocket propulsion systems. In this Account, we review recent experimental work in which gas phase organo boronyl monomers (RBO) are formed via bimolecular reactions of the boronyl radical (BO) with C2-C6 unsaturated hydrocarbons. The investigated hydrocarbons are widely exploited as fuels, and their reactions with boronyl radicals under single collision conditions lead to the formation of organo boronyls. Our studies also elucidate the mechanisms of their formation reactions thus furnishing a comprehension at the molecular level of this reaction class. The variety of the employed hydrocarbon substrates has allowed us to systematically classify the chemical behavior of the boronyl radicals. With the exception of the case of the dimethylacetylene reaction, the boron monoxide radical versus atomic hydrogen exchange mechanisms were always open leading to the formation of highly unsaturated organo boronyl monomers (RBO), which could be easily identified because they cannot trimerize under single collision conditions. Besides the hydrogen displacement pathway, methylacetylene, dimethylacetylene, and propylene, carrying one or two methyl groups, were also found to eliminate a methyl group. In all systems, the reactions were barrierless, indirect, and initiated by addition of the boron monoxide radical to the π electron density of the hydrocarbon molecule, with the radical center located at the boron atom of the BO radical, thus leading to doublet radical intermediates. These intermediates either decompose via hydrogen or methyl loss or isomerize prior to their decomposition via atomic hydrogen or migration of the BO moiety. A consistent trend suggests that all exit transition states are rather tight with those involved in the hydrogen atom loss depicting exit barriers of typically 25 to 35 kJ mol-1, whereas the methyl loss pathways are associated with tighter exit transition states located about 30-50 kJ mol-1above the separated products. Further, the overall energetics suggest that those bimolecular reactions are exoergic by 40-90 kJ mol-1. These findings confirm that this reaction class leads to the formation of highly unsaturated organo boronyl molecules.
authors.affiliation: Department of Chemistry, University of Hawaii at Manoa , Honolulu, Hawaii 96822, United States.
authors.forename: Ralf I
authors.identifier: 0000-0002-7233-7206
authors.initials: RI
authors.lastname: Kaiser
authors.affiliation: Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia , 06123 Perugia, Italy.
authors.forename: Nadia
authors.initials: N
authors.lastname: Balucani