Double Bond Cleavage in Small Molecules Using a Geminal Sc/P Lewis Pair
Guan, Yiwen, Xu, Xian, Xu, Xin*(徐信)
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China.
Inorg. Chem 2023, 62, 14782-14789
Abstract：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 rareearth metal complexes to capture reactive species.
链接：//pubs.acs.org/doi/10.1021/acs.inorgchem.3c02263
