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Precise Activation of Ammonia and Carbon Dioxide by an Iminodisilene
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-07-15 , DOI: 10.1002/anie.201804472 Daniel Wendel 1 , Tibor Szilvási 2 , Daniel Henschel 1 , Philipp J. Altmann 3 , Christian Jandl 3 , Shigeyoshi Inoue 4 , Bernhard Rieger 1
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-07-15 , DOI: 10.1002/anie.201804472 Daniel Wendel 1 , Tibor Szilvási 2 , Daniel Henschel 1 , Philipp J. Altmann 3 , Christian Jandl 3 , Shigeyoshi Inoue 4 , Bernhard Rieger 1
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The activation of NH3 and CO2 is still an ambitious target for multiply bonded sub‐valent silicon compounds. Now, the precise splitting of the N−H bond of ammonia by (Z)‐imino(silyl)disilene 1 to give trans‐1,2‐adduct 2 a at low temperatures (−78 °C) is presented. According to DFT calculations, the stereospecific hydroamination follows a similar mechanism as the recently reported anti‐addition of H2 to the Si=Si bond of 1. The aminosilane 2 b could also be obtained as the formal silylene addition product under thermodynamic reaction control. By applying low temperatures, the activation of CO2 with 1 selectively afforded the cis‐oxadisilacyclobutanone 7‐c as [2+2] cycloadduct. By performing the reaction directly at ambient temperatures, a mixture of three different‐sized silacycles (4–6) was observed. Their formation was investigated theoretically and their structures were revealed with separate experiments using 1 and the oxygenation agents N2O and O2.
中文翻译：
亚氨基二ilene精确活化氨和二氧化碳
NH 3和CO 2的活化仍然是多重键合亚价硅化合物的雄心勃勃的目标。现在，提出了在低温（-78°C）下，（Z）-亚氨基（甲硅烷基）二ilenene 1对氨的NH键的精确裂解，从而得到反式1,2-加合物2a。根据DFT计算，立体有择加氢胺化遵循类似的机制为最近报道抗添加H 2到的所述Si = Si键1。在热力学反应控制下，氨基硅烷2b也可以作为正式的亚甲硅烷基加成产物获得。通过施加低温，用1活化CO 2有选择地提供了顺式-恶二硅环环丁酮7-c作为[2 + 2]环加合物。通过直接在环境温度下进行反应，可以观察到三种不同大小的硅杂环化合物（4 – 6）的混合物。从理论上研究了它们的形成，并使用1和氧合剂N 2 O和O 2分别进行了实验，揭示了它们的结构。
更新日期：2018-07-15
中文翻译：
亚氨基二ilene精确活化氨和二氧化碳
NH 3和CO 2的活化仍然是多重键合亚价硅化合物的雄心勃勃的目标。现在，提出了在低温（-78°C）下，（Z）-亚氨基（甲硅烷基）二ilenene 1对氨的NH键的精确裂解，从而得到反式1,2-加合物2a。根据DFT计算，立体有择加氢胺化遵循类似的机制为最近报道抗添加H 2到的所述Si = Si键1。在热力学反应控制下，氨基硅烷2b也可以作为正式的亚甲硅烷基加成产物获得。通过施加低温，用1活化CO 2有选择地提供了顺式-恶二硅环环丁酮7-c作为[2 + 2]环加合物。通过直接在环境温度下进行反应，可以观察到三种不同大小的硅杂环化合物（4 – 6）的混合物。从理论上研究了它们的形成，并使用1和氧合剂N 2 O和O 2分别进行了实验，揭示了它们的结构。
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