Formation of an Azaruthenacyclopentadiene Skeleton via Ammonia Activation by an Electron‐Deficient Ru <sub>3</sub> Cluster
Formation of an Azaruthenacyclopentadiene Skeleton via Ammonia Activation by an Electron‐Deficient Ru <sub>3</sub> Cluster
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缺电子 Ru <sub>3</sub> 簇通过氨活化形成氮杂环戊二烯骨架
DOI：
10.1002/chem.202200327
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Kai Masataka
中科院分区：
文献类型：
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作者：
Takao Toshiro;Takahashi Yuta;Kai Masataka
含有μ3-η3-C3环的双阳离子三钌配合物[（Cp*Ru）3（μ3-η3-C3 MeH 2-）（μ3-CH）（μ-H）]2+（1 a，Cp*=η5-C5 Me 5）与氨反应，通过N-H键断裂产生μ-酰胺配合物[（Cp*Ru）3（μ3-η3-CHCMeCH）（μ3-CH）（μ-NH 2）]2+（5）。随后用碱处理导致C-N键形成，得到μ3-η2：η2 - 1-氮杂丁二烯-4-基络合物[（Cp*Ru）3（μ3-CH）（μ3-η2：η2-NH= CH-CMe =CH-）]+（6 a）。在氨存在下，通过单阳离子配合物[（Cp*Ru）3（μ3-η3-C3 RH 2-）（μ3-CH）]+（2 a; R=Me，2 B; R=H）的光解交替合成了氮杂钌并环戊二烯骨架. C3环骨架通过电子转移到C3环中的π*（C-C）轨道而断裂，并且瞬时产生的不饱和μ3-烯丙基物质可以吸收氨，导致N-H键断裂，随后形成C-N键。
A dicationic triruthenium complex containing aμ3‐η3‐C3ring, [(Cp*Ru)3(μ3‐η3‐C3MeH2−)(μ3‐CH)(μ‐H)]2+(1 a, Cp*=η5‐C5Me5), reacted with ammonia to yield aμ‐amido complex, [(Cp*Ru)3(μ3‐η3‐CHCMeCH) (μ3‐CH)(μ‐NH2)]2+(5), via N−H bond scission. Subsequent treatment with base resulted in C−N bond formation to yield aμ3‐η2:η2‐1‐azabutadien‐4‐yl complex, [(Cp*Ru)3(μ3‐CH)(μ3‐η2:η2‐NH=CH−CMe=CH−)]+(6 a). The azaruthenacyclopentadiene skeleton was alternatively synthesized by the photolysis of mono‐cationic complex [(Cp*Ru)3(μ3‐η3‐C3RH2−)(μ3‐CH)]+(2 a; R=Me,2 b; R=H) in the presence of ammonia. The C3ring skeleton was broken via the electron transfer to theπ*(C−C) orbital in the C3ring, and a transiently generated unsaturatedμ3‐allylic species can take up ammonia, resulting in N−H bond scission followed by C−N bond formation.