The diaryldiselenides reacted with titanocene hydried (Cp2TiH) generted from Cp2TiCl2/i-BuMgBr to give arylselenium complexes of titanocene. They reacted readily with diaryliodoiums salt to give unsymmetical diaryls...The diaryldiselenides reacted with titanocene hydried (Cp2TiH) generted from Cp2TiCl2/i-BuMgBr to give arylselenium complexes of titanocene. They reacted readily with diaryliodoiums salt to give unsymmetical diarylselenides.展开更多
Reduction of diaryldiselenides by the system of Cp2TiCl2/Bu'MgBr/THF gave the nucleophilic arylselenium complex. They reacted with diaryl iodonium salts to afford unsymmetrical diaryl selenides in high yields.
基金Project 29672008 was supported by NationalNatural Science Foundation of China.
文摘The diaryldiselenides reacted with titanocene hydried (Cp2TiH) generted from Cp2TiCl2/i-BuMgBr to give arylselenium complexes of titanocene. They reacted readily with diaryliodoiums salt to give unsymmetical diarylselenides.
文摘Reduction of diaryldiselenides by the system of Cp2TiCl2/Bu'MgBr/THF gave the nucleophilic arylselenium complex. They reacted with diaryl iodonium salts to afford unsymmetrical diaryl selenides in high yields.
文摘制备了6种不同结构的二芳基碘鎓盐。通过近红外光谱测定环氧树脂(E-51)在碘鎓盐引发下的环氧转换率,系统考察了在395 nm LED光源辐照下,取代基对二芳基碘鎓盐引发E-51光聚合的影响。通过密度泛函理论对合成的6种碘鎓盐进行分子优化,发现不同的取代基对二芳基碘鎓盐的最低未占分子轨道能级和最高占据分子轨道能级均会产生影响。电化学测试发现,取代基通过对碘鎓盐的还原电势产生影响,进而影响其与光敏剂间的光电荷转移能力。根据Rehm-Weller公式,计算得到了不同取代基的碘鎓盐与异丙基蒽酮间电荷转移的自由能,它们之间的自由能变化值分别为-1.017、-0.720、-0.664、-0.577、-1.140和-0.915 e V,从热力学上讨论了电荷转移的可能性。研究发现不同烷基取代基的碘鎓盐中,烷基空间位阻越小,其光引发速率越快;当碘鎓盐芳环上连接吸电子基团时,光引发速率提高。