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Silicon and Oxygen’s Bond of Affection: An Acyclic Three-Coordinate Silanone and Its Transformation to an Iminosiloxysilylene
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-11-16 00:00:00 , DOI: 10.1021/jacs.7b10634 Daniel Wendel 1 , Dominik Reiter 1 , Amelie Porzelt 1 , Philipp J. Altmann 1 , Shigeyoshi Inoue 1 , Bernhard Rieger 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-11-16 00:00:00 , DOI: 10.1021/jacs.7b10634 Daniel Wendel 1 , Dominik Reiter 1 , Amelie Porzelt 1 , Philipp J. Altmann 1 , Shigeyoshi Inoue 1 , Bernhard Rieger 1
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A long-term dream comes true: An acyclic, neutrally charged silanone at last! Here, we report on the first examples of isolable acyclic, neutral, three-coordinate silanones 2 with indefinite stability as solids and lifetimes in solution of up to 2 days. The electronic properties of the Si═O bond were investigated via DFT calculations and revealed the π-donating N-heterocyclic imino (NHI) and σ-donating silyl groups as key factors for their enhanced stability. Besides initial reactivity studies of 2 toward CO2 and methanol, different isomerization pathways depending on the silyl substitution pattern were found. For 2a (R = TMS), a 1,3-silyl shift gave an intermediary disilene, which was trapped as unique NHC-disilene adduct 6. For the more stable silanone 2b (R = t-Bu), a selective transformation to the first reported room temperature stable, acyclic, two-coordinate N,O-silylene 7 exhibiting a fascinating siloxy ligand was observed. Both compounds were fully characterized experimentally and their bonding features were analyzed by theoretical calculations.
中文翻译：
硅与氧的键合关系：无环三配位硅酮及其向氨基硅氧基甲硅烷基的转化
一个长期的梦想成真：无环，中性电荷的硅酮终于实现了！在这里，我们报告了可分离的无环，中性，三坐标硅烷酮2的第一个实例，该溶液具有不确定的固体稳定性和在溶液中长达2天的寿命。通过DFT计算研究了Si═O键的电子性质，发现π供电的N杂环亚氨基（NHI）和σ供电的甲硅烷基是提高稳定性的关键因素。除了最初对2对CO 2和甲醇的反应性研究以外，还发现了不同的异构化途径，具体取决于甲硅烷基的取代方式。对于2a（R = TMS），一个1,3-甲硅烷基转移得到一个中间的二甲苯，被困为独特的NHC-二甲苯加合物6。对于更稳定的硅酮2b（R = t -Bu ），观察到选择性转化为第一个报道的室温下稳定的，无环的，二配位的N，O-亚甲硅烷基7，其表现出令人着迷的甲硅烷氧基配体。两种化合物均经过实验充分表征，并通过理论计算分析了它们的键合特征。
更新日期：2017-11-17
中文翻译：
硅与氧的键合关系：无环三配位硅酮及其向氨基硅氧基甲硅烷基的转化
一个长期的梦想成真：无环，中性电荷的硅酮终于实现了！在这里，我们报告了可分离的无环，中性，三坐标硅烷酮2的第一个实例，该溶液具有不确定的固体稳定性和在溶液中长达2天的寿命。通过DFT计算研究了Si═O键的电子性质，发现π供电的N杂环亚氨基（NHI）和σ供电的甲硅烷基是提高稳定性的关键因素。除了最初对2对CO 2和甲醇的反应性研究以外，还发现了不同的异构化途径，具体取决于甲硅烷基的取代方式。对于2a（R = TMS），一个1,3-甲硅烷基转移得到一个中间的二甲苯，被困为独特的NHC-二甲苯加合物6。对于更稳定的硅酮2b（R = t -Bu ），观察到选择性转化为第一个报道的室温下稳定的，无环的，二配位的N，O-亚甲硅烷基7，其表现出令人着迷的甲硅烷氧基配体。两种化合物均经过实验充分表征，并通过理论计算分析了它们的键合特征。
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