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381.
Toshiaki Murai Tomoyoshi Mizutani Takahiro Kanda Shinzi Kato 《Heteroatom Chemistry》1995,6(3):241-246
Aromatic diselenoic acid Se-methyl esters 1 react with amines at 0°C in tetrahydrofuran (THF) to yield selenoamides in moderate to good yields. The reaction course is highly dependent on the steric requirements of both starting materials. In the reactions of the ester 1a with 2-methylpiperidine and of the ester 1b with piperidine, the starting materials disappear within 1 hour with the liberation of black selenium, but the corresponding selenoamides are not produced. These results may be ascribed to the steric congestion caused by the formation of the selenoamide group from the tetrahedral intermediate 15 . X-ray crystal structure analyses of the selenoamides 3 and 9 have been performed. The bond length of C(Se) N is shorter than a carbon nitrogen single bond. On the other hand, the CSe bond is longer than that of the ordinary carbon-selenium double bond. These results are indicative of the efficient delocalization of the electrons of nitrogen to the carbon–selenium double bond. The double bond character between the carbon attached to selenium and the nitrogen is also supported by the nitrogen atom showing sp2 character. When a methyl group is introduced at the meta position of the aromatic ring, the deviation of the aromatic ring from the plane involving the carbon–selenium double bond and nitrogen atom becomes substantially large, perhaps due to the steric bulkiness of the selenium atom. 相似文献
382.
383.
Keisuke Shigenobu Taku Sudoh Junichi Murai Kaoru Dokko Masayoshi Watanabe Kazuhide Ueno 《Chemical record (New York, N.Y.)》2023,23(8):e202200301
Highly concentrated electrolytes (HCEs) have a similarity to ionic liquids (ILs) in high ionic nature, and indeed some of HECs are found to behave like an IL. HCEs have attracted considerable attention as prospective candidates for electrolyte materials in future lithium secondary batteries owing to their favorable properties both in the bulk and at the electrochemical interface. In this study, we highlight the effects of the solvent, counter anion, and diluent of HCEs on the Li+ ion coordination structure and transport properties (e. g., ionic conductivity and apparent Li+ ion transference number measured under anion-blocking conditions, ). Our studies on dynamic ion correlations unveiled the difference in the ion conduction mechanisms in HCEs and their intimate relevance to values. Our systematic analysis of the transport properties of HCEs also suggests the need for a compromise to simultaneously achieve high ionic conductivity and high values. 相似文献