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null (Ed.)Broadband microwave spectra have been recorded for weakly bound clusters formed from mixtures containing fluoroethylene (FE) or 1,1-difluoroethylene (DFE) and varying percentages of CO2. These clusters serve as simple models for behavior of supercritical CO2 as a solvent. Analysis of changes in rotational transition intensities as CO2 concentration is systematically varied allows identification and assignment of spectra for a multitude of different clusters from within a single data set, with at least 15 species identified in FE/CO2 mixtures, and 4 species so far identified in DFE/CO2 mixtures. Several analysis approaches have been implemented, ranging from simple correlation of intensity variations between two spectra recorded with different sample concentrations, to more sophisticated principal component analysis based representations of the spectroscopic data from multiple scans. These techniques provide a range of tools that, in addition to facilitating assignment of spectra of complex mixtures, also assist in identifying the chemical species that give rise to the spectra within each mixture. The visual aspects of the research process, and the accessibility of coding tools such as Python, Excel and Mathcad, make this work particularly appropriate to undergraduate students, including those with little or no previous physical chemistry experience.more » « less
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Trammel, Grace L.; Kannangara, Prashansa B.; Vasko, Dmytro; Datsenko, Oleksandr; Mykhailiuk, Pavel; Brown, M. Kevin (, Angewandte Chemie International Edition)Abstract Two catalytic systems have been developed for the arylboration of endocyclic enecarbamates to deliver synthetically versatile borylated saturated N‐heterocycles in good regio‐ and diastereoselectivities. A Cu/Pd dual catalytic reaction enables the synthesis of borylated, α‐arylated azetidines, while a Ni‐catalysed arylboration reaction efficiently functionalizes 5‐, 6‐, and 7‐membered enecarbamates. In the case of the Cu/Pd‐system, a remarkable additive effect was identified that allowed for broader scope. The products are synthetically useful, as demonstrated by manipulations of the boronic ester to access biologically active compounds.more » « less
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Kannangara, Prashansa B.; West, Channing T.; Peebles, Sean A.; Peebles, Rebecca A. (, Chemical Physics Letters)
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