Zhang Xin, Liu Liu Leo
Department of Chemistry and Research Center for Chemical Biology and Omics Analysis, College of Science, Southern University of Science and Technology, Shenzhen 518055, China.
State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China.
J Am Chem Soc. 2023 Jul 26;145(29):15729-15734. doi: 10.1021/jacs.3c05954. Epub 2023 Jul 17.
Neutral aluminum chalcogenides (R-Al(L)═Ch; L = ligand, Ch = chalcogen), stabilized by a Lewis base ligand, represent isoelectronic counterparts to carbonyl compounds and have long been pursued for isolation. Herein, we present the synthesis of an aluminum selenide, [N]-Al(Pr-bimy)═Se, and an aluminum telluride, [N]-Al(Pr-bimy)═Te, under ambient conditions ([N] = 1,8-bis(3,5-di--butylphenyl)-3,6-di--butylcarbazolyl; Pr-bimy = 1,3-diisoproplylbenzimidazole-2-ylidene). These compounds arise from the oxidation reaction of [N]-Al(Pr-bimy) with Se and (Bu)P═Te, respectively. One notable characteristic of the Al and Ch interaction is the presence of an Al-Ch σ bond, strengthened by the electrostatic attraction between the Al and Ch centers as well as the donation of lone pairs from Ch into vacant orbitals at Al. This results in an Al-Ch multiple bond with an ambiphilic nature. Preliminary investigations into their reactivity unveil their remarkable propensity for facile (cyclo)addition reactions with diverse substrates, including PhCCH, PhCN, AdN, MeI, PhSiH, and CF, leading to the formation of unprecedented main group heterocycles and alumachalcogenides.
由路易斯碱配体稳定的中性铝硫属化物（R - Al(L)═Ch；L = 配体，Ch = 硫属元素）是羰基化合物的等电子体对应物，长期以来一直致力于其分离。在此，我们展示了在环境条件下（[N] = 1,8 - 双(3,5 - 二叔丁基苯基)-3,6 - 二叔丁基咔唑基；Pr - bimy = 1,3 - 二异丙基苯并咪唑 - 2 - 亚基）合成硒化铝 [N]-Al(Pr - bimy)═Se 和碲化铝 [N]-Al(Pr - bimy)═Te。这些化合物分别由 [N]-Al(Pr - bimy) 与 Se 和 (Bu)P═Te 的氧化反应生成。Al 与 Ch 相互作用的一个显著特征是存在 Al - Ch σ键，该键通过 Al 和 Ch 中心之间的静电吸引以及 Ch 的孤对电子向 Al 的空轨道的捐赠而得到加强。这导致形成具有双亲性质的 Al - Ch 多重键。对它们反应性的初步研究揭示了它们与多种底物（包括 PhCCH、PhCN、AdN、MeI、PhSiH 和 CF）进行 facile（环）加成反应的显著倾向，从而导致形成前所未有的主族杂环和铝硫属化物。
