A Stable Cyclic (R2SnAu)3 Anion Having In-Plane σ-Mobius Aromaticity
A Stable Cyclic (R2SnAu)3 Anion Having In-Plane σ-Mobius Aromaticity
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具有面内西格玛-莫比乌斯芳香性的稳定环状(R2SnAu)(3)阴离子
DOI：
10.1002/anie.201910731
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发表时间：
2019-12-17
影响因子：
16.6
通讯作者：
Li, Zhifang
中科院分区：
文献类型：
--
作者：
Wang, Liliang;Xu, Jian;Li, Zhifang
通过稳定的二烷基亚锡基1与R '3 PAuCl（R '=Et，Ph）反应，然后用KCl 8还原，合成了一种稳定的环状（R2 SnAu）（3）阴离子（3（-），R2 Sn = 2，2，5，5-四（三甲基硅基）-1-锡环戊烷-1，1-二基）与K+（THF）（6）的蓝色盐。晶体结构和核磁共振分析表明，3（-）的六元（SnAu）（3）环是平面的，六个Au-Sn键间距相等，具有高度对称性。3（-）在己烷中的UV/维斯光谱显示在598 nm处有强吸收。虽然具有四价电子的环状Au-3（-）被认为是不稳定的反芳族阴离子，但具有三个二价锡配体的3（-）是稳定的σ芳族阴离子，具有前所未有的Mobius轨道阵列，如3（-）的微扰MO和CCSD分析所预测的。
A cyclic (R2SnAu)(3) anion (3(-), R2Sn=2,2,5,5-tetrakis(trimethylsilyl)-1-stannacyclopentane-1,1-diyl) has been synthesized as a stable blue salt with K+(THF)(6) through the reaction of stable dialkylstannylene 1 with R ' 3PAuCl (R '=Et, Ph) followed by the reduction with KC8. Crystallographic and NMR analysis shows that the six-membered (SnAu)(3) ring of 3(-) is planar and highly symmetric with an equal distance of six Au-Sn bonds. A UV/Vis spectrum of 3(-) in hexane reveals an intense absorption maximum at 598 nm. While cyclic Au-3(-) with four valence electrons is known as unstable anti-aromatic anion, 3(-) with three divalent tin ligands is stable sigma aromatic anion with an unprecedented Mobius orbital array as predicted by the perturbation MO and CCSD analysis of 3(-).