File(s) under embargo
Reason: Pending Publications
until file(s) become available
REACTIVITY STUDIES OF QUINOLINE- AND ACRIDINIUM-BASED POLYRADICALS IN THE GAS PHASE
thesisposted on 31.01.2022, 15:37 by Duanchen DingDuanchen Ding
Positively charged aromatic carbon-centered σ-type mono-and biradicals have been studied previously in the gas phase. However, very little is known about the properties of related polyradicals. In this dissertation, the reactions of series of quinolinium-and acridinium-based bi-, tri-, and tetraradicals were studied with cyclohexane and allyl iodide in the gas phase by using tandem mass spectrometry. I atom abstraction and allyl group abstraction were observed as dominant reactions for all the studied radicals upon reactions with allyl iodide. Sequential H atom abstractions were observed as the major reactions for the studied bi-and tetraradicals upon reactions with cyclohexane. Surprisingly, triradicals appeared to undergo addition followed by elimination of a H atom as one of the major reactions upon interactions with cyclohexane. Vertical electron affinity and spin-spin coupling between radical sites were found to control the radical reactivities.
The radical site(s) which react first with cyclohexane were experimentally determined. For the studied biradicals, the first reacting radical sites were found to be the ones that are predicted to be more reactive based on the reactivities of related monoradicals. For the studied triradicals, the first reacting radical sites are the ones that are least strongly coupled to the other radical sites. For tetraradicals, the first two sites reacting with cyclohexane are more weakly coupled than the other two radical sites.
The mechanisms for the reactions of the triradicals with cyclohexane were proposed based on tandem mass spectrometry experiments and supported by quantum chemical calculations. Briefly, the least strongly coupled radical site of a triradical reacts with cyclohexane first by abstracting a H atom. The more reactive radical site insome of the produced biradicals will then abstract a H atom from the cyclohexyl radical within the product collision complex to generate a monoradical and cyclohexene. Some of these monoradicals undergo addition to cyclohexene within this product complex,followed by elimination of a H atom. When allowed to react with allyl iodide, all of the monoradicals and most of the biradicals demonstrated predominant I atom abstraction. The quinolinium-based meta-and para-benzynes exhibited allyl group abstraction as the major reaction. The triradicals with a meta-benzyne moiety in the pyridinium ring demonstrated dominant allyl group abstraction, which is likely to occur at the pyridinium moiety. The reaction efficienciesof these triradicals toward allyl iodide are correlated with their calculated vertical electron affinities. The other triradicals showed I atom abstraction as the major reaction. These triradicals react with allyl iodide through different mechanisms compared to those mainly abstract an allyl group. Therefore, their reactivities are not directly related to their calculated vertical electron affinities.
In the tetraradicals, spin-spin coupling between all the radical sites affects their reactivities. The coupling of the radicals in a benzyne moiety is weakened by the couplings of radical sites between two benzyne moieties. This interaction results in higher reaction efficiencies for the tetraradicals than the related benzynes. Particularly, the 2,4,7,8-tetradehydroquinolinium cation was found to have much higher reactivity than the related meta-benzyne, the 2,4-didehydroquinolinium cation. This was rationalized based on the low distortion energy of the meta-benzyne moiety in the tetraradical.
Spin-spin coupling between the radical sites in bi-, tri-, and tetraradicals significantly affect their reactivity. To better understand the relation between the effects of spin-spin coupling and the spatial distance between two radical sites, a series of acridinium-based mono-and biradicals were studied in the gas phase. The acridinium-based monoradicals are less reactive than the related quinolinium-based monoradicals, which is possibly because of the steric hindrance of the additional benzene ring. Unlike quinolinium-based biradicals, which are less reactive than the related monoradicals, acridinium-based biradicals showed higher reactivities than the monoradicals with similar vertical electron affinities. In order to better illustrate the coupling strength in the studied biradicals, the natural logarithm of their total reaction efficiencies toward cyclohexane was plotted as a function of their calculated vertical electron affinities. The plots indicate that the coupling of quinolinium-based biradicals hinders the radical reactivity, while for acridinium-based biradicals, the coupling is negligibly weak and the biradicals react as two individual monoradicals.
Gas-phase and Solution Reactivity Studies on para-Benzyne Analogs and Related Bi, Tri- and Tetraradicals
Directorate for Mathematical & Physical SciencesFind out more...