Double Bond Cleavage in Small Molecules Using a Geminal Sc/P Lewis Pair.

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) 2 ScN( t Bu)PPh 2 (Ar = 2,6- t Bu 2 -C 6 H 3 ), that exhibits typical FLP-type 1,2-addition reactivity toward CO 2 . 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.