Sahoo Padmini, Majumdar Moumita
Department of Chemistry, Indian Institute of Science Education and Research, Pune-411008, Maharashtra, India.
Dalton Trans. 2022 Jan 25;51(4):1281-1296. doi: 10.1039/d1dt03331j.
The reductively disilylated N-heterocyclic systems 1,4-bis(trimethylsilyl)-1-aza-2,5-cyclohexadiene (1Si), 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine (2Si) and its methyl derivatives (3Si and 4Si), and 1,1'-bis(trimethylsilyl)-4,4'-bipyridinylidene (5Si) are proficient organosilicon reagents owing to their low first vertical ionization potentials and the heterophilicity of the polarized N-Si bonds. These have prompted their reactivity as two-electron reductants or reductive silylations. These reactions benefit from the concomitant rearomatization of the N-heterocycles and liberation of trimethylsilyl halides or (MeSi)O, which are mostly volatile or easily removable byproducts. In this perspective, we have discussed the utilization of these reductively disilylated N-heterocyclic systems as versatile reagents in the salt-free reduction of transition metals (A) and main-group halides (B), in organic transformations (C) and in materials syntheses (D).
经还原二硅化的氮杂环体系，如1,4 - 双（三甲基硅基）-1 - 氮杂 - 2,5 - 环己二烯（1Si）、1,4 - 双（三甲基硅基）-1,4 - 二氢吡嗪（2Si）及其甲基衍生物（3Si和4Si），以及1,1'-双（三甲基硅基）-4,4'-联吡啶叉（5Si），由于其较低的第一垂直电离势以及极化N - Si键的亲异性，是高效的有机硅试剂。这些特性促使它们作为双电子还原剂或还原硅烷化试剂发生反应。这些反应得益于氮杂环的伴随再芳构化以及三甲基硅基卤化物或（MeSi）O的释放，这些大多是挥发性的或易于除去的副产物。从这个角度出发，我们讨论了这些经还原二硅化的氮杂环体系作为通用试剂在过渡金属（A）和主族卤化物（B）的无盐还原、有机转化（C）以及材料合成（D）中的应用。
