Spin-spin Coupling Controls the Gas-phase Reactivity of Aromatic σ-Type Triradicals.

Examination of the reactions of σ-type quinolinium-based triradicals with cyclohexane in the gas phase demonstrated that the radical site that is the least strongly coupled to the other two radical sites reacts first, independent of the intrinsic reactivity of this radical site, in contrast to related biradicals that first react at the most electron-deficient radical site. Abstraction of one or two H atoms and formation of an ion that formally corresponds to a combination of the ion and cyclohexane accompanied by elimination of a H atom ("addition - H") were observed. In all cases except one, the most reactive radical site of the triradicals is intrinsically less reactive than the other two radical sites. The product complex of the H abstraction either dissociates to give the H atom abstraction product and the cyclohexyl radical or the more reactive radical site in the produced biradical abstracts a H atom from the cyclohexyl radical. The monoradical product can add to cyclohexene followed by elimination of a H atom, generating the "addition - H" products. Similar reaction efficiencies were measured for three of the triradicals as for relevant monoradicals. Surprisingly, the remaining three triradicals (all with a meta -pyridyne moiety) reacted substantially faster than the relevant monoradicals . This is rationalized based on the exothermic generation of the same meta -pyridyne analog for these three triradicals has enough energy to attain the dehydrocarbon atom separation common for H atom abstraction transition states of protonated meta -pyridynes.