锆氮杂环丙烷离子对H的活化作用：σ键复分解与受阻路易斯酸碱对反应活性
H activation by zirconaziridinium ions: σ-bond metathesis versus frustrated Lewis pair reactivity.
作者信息
Budzelaar Peter H M, Hughes David L, Bochmann Manfred, Macchioni Alceo, Rocchigiani Luca
机构信息
Department of Chemistry, University of Naples Federico II, Via Cintia, I-80126, Naples, Italy.
出版信息
Chem Commun (Camb). 2020 Feb 28;56(17):2542-2545. doi: 10.1039/c9cc09466k. Epub 2020 Feb 4.
Zirconaziridinium ions [CpZr(η-CHNR)] can potentially activate H by two routes: σ-bond metathesis or FLP reactivity. We show here that Zr-C hydrogenolysis by σ-bond metathesis precedes and enables subsequent heterolytic H cleavage through FLP pathways. DFT calculations show the involvement of transition states with approximately linear NHH and bent ZrHH arrangements without any direct Zr-amine interaction.
锆氮丙啶离子[CpZr(η-CHNR)] 可能通过两种途径活化氢：σ键复分解或FLP反应性。我们在此表明，通过σ键复分解进行的Zr-C氢解先于并通过FLP途径实现随后的异裂氢裂解。密度泛函理论计算表明，过渡态的参与具有近似线性的NHH和弯曲的ZrHH排列，且没有任何直接的Zr-胺相互作用。
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