Aromatic Selenoic, Selenothioic, and Diselenoic Acid Salts: Isolation, Characterization, and Se-77 NMR Spectra, Together with Theoretical Elucidation

作者：Murai Toshiaki^*; Nishi Daisuke; Hayashi Satoko; Nakanishi Waro

来源：Bulletin of the Chemical Society of Japan, 2014, 87(6): 677-692.

DOI：10.1246/bcsj.20140018

To systematically elucidate molecular and electronic structures of aromatic selenoic acid salts and their heavier congeners, they were synthesized by reacting selenoic, selenothioic, and diselenoic acid Se-[2-(trimethylsilyl)ethyl] esters with ammonium fluorides. The resulting salts were characterized by C-13 and Se-77 NMR spectra, and some of their molecular structures were disclosed by X-ray analyses. These results were compared with spectroscopic properties and molecular structures of selenoic and selenothioic acid Se-methyl esters. As a result, in the resonance hybrids of selenoic and selenothioic acid ammonium salts, the resonance structures involving carbon-selenium double bonds also contribute to the resonance hybrids, and the importance of these resonance structures appears to increase on going from selenoic to selenothioic acid salts on the basis of the results of the coupling constants of carbon-selenium bonds and UV-visible spectra. The results were well supported by the optimized structures and evaluated NMR parameters for the species.

• 出版日期2014-6-15