Double Bond Cleavage in Small Molecules Using a Geminal Sc/P Lewis Pair,Inorganic Chemistry

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Double Bond Cleavage in Small Molecules Using a Geminal Sc/P Lewis Pair
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2023-08-29 , DOI: 10.1021/acs.inorgchem.3c02263
Yiwen Guan ₁ , Xian Xu ₁ , Xin Xu ₁

Affiliation

Frustrated Lewis pairs (FLPs) have proven capable of cleaving the H–H σ-bond and binding a variety of unsaturated small molecules. In contrast, examples of FLP-mediated complete rupture of double-bonded substrates remain scarce. Herein, we present a geminal Sc/P Lewis pair, i.e., (ArO)₂ScN(^tBu)PPh₂ (Ar = 2,6-^tBu₂-C₆H₃), that exhibits typical FLP-type 1,2-addition reactivity toward CO₂. Notably, it enables the complete cleavage of a series of double bonds, such as the N═N bond in azobenzene or pyridazine, the N═O bond in nitrosobenzene, and the N═S and S═O bonds in N-sulfinylaniline, to yield the corresponding metallacyclic products. Moreover, the first rare-earth metal sulfur monoxide adduct could be obtained through the bond cleavage of PhNSO, demonstrating the capability of rare-earth metal complexes to capture reactive species.

中文翻译：

使用双 Sc/P 路易斯对在小分子中进行双键断裂

受阻路易斯对 (FLP) 已被证明能够裂解 H–H σ 键并结合各种不饱和小分子。相比之下，FLP 介导的双键基底完全断裂的例子仍然很少。在此，我们提出了孪生Sc/P路易斯对，即(ArO) ₂ ScN( ^t Bu)PPh ₂ (Ar = 2,6- ^t Bu ₂ -C ₆ H ₃ )，其表现出典型的FLP-type 1， CO ₂的2-加成反应性。值得注意的是，它能够完全裂解一系列双键，例如偶氮苯或哒嗪中的N=N键、亚硝基苯中的N=O键以及N-亚磺酰基苯胺中的N=S和S=O键，从而得到相应的金属环产物。此外，通过PhNSO的键断裂可以得到第一个稀土金属一氧化硫加合物，证明了稀土金属配合物捕获活性物质的能力。

更新日期：2023-08-29

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