Maltz Logan T, Gabbaï François P
Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States.
Organometallics. 2024 May 29;43(11):1246-1255. doi: 10.1021/acs.organomet.4c00094. eCollection 2024 Jun 10.
With an interest in chalcogen bonding, we use a rigid indazolium backbone to install a formally zero-valent Se center next to a divalent Te center, allowing us to investigate the effects of oxidation of the Se center on the observed Te···Se interaction. Through spectroscopic and computational comparison of the Se(0) species with its Se(II) counterpart and their monochalcogen analogues, we experimentally and computationally investigate the effect of modulating Se basicity on the resulting Te···Se interaction. Comparison with well-studied naphthalene and acenaphthene variants indicates that the increased basicity of the Se(0) center allows for a comparably strong Te···Se interaction despite longer distances and a larger splay angle. Finally, our study illuminates the potential non-innocence of cationic organic substituents in chalcogen-bonding catalysis of the transfer hydrogenation of quinolines.
出于对硫族元素键合的兴趣，我们使用刚性吲唑鎓骨架在二价碲中心旁边安装一个形式上零价的硒中心，从而能够研究硒中心氧化对观察到的碲···硒相互作用的影响。通过将硒（0）物种与其硒（II）对应物及其单硫族类似物进行光谱和计算比较，我们从实验和计算上研究了调节硒碱度对所得碲···硒相互作用的影响。与经过充分研究的萘和苊变体的比较表明，尽管距离更长且张开角更大，但硒（0）中心碱度的增加使得碲···硒相互作用相当强。最后，我们的研究揭示了阳离子有机取代基在喹啉转移氢化的硫族元素键合催化中可能并非无害。
