Cooperative Bond Activation and Catalytic CO₂ Functionalization with a Geometrically Constrained...

Metal-ligand cooperativity has emerged as an important strategy to tune the reactivity of transition-metal complexes for the catalysis and activation of small molecules. Studies of main-group compounds, however, are scarce. Here, we report the synthesis, structural characterization, and reactivity of a geometrically constrained bis(silylene)-stabilized borylene. The one-pot reaction of [(SiNSi)Li(OEt₂)] (SiNSi = 4,5-bis(silylene)-2,7,9,9-tetramethyl-9H-acridin-10-ide) with 1 equiv of [BBr₃(SMe₂)] in toluene at room temperature followed by reduction with 2 equiv of potassium graphite (KC₈) leads to borylene [(SiNSi)B] (1), isolated as blue crystals in 45% yield. X-ray crystallography shows that borylene (1) has a tricoordinate boron center with a distorted T-shaped geometry. Computational studies reveal that the HOMO of 1 represents the lone pair orbital on the boron center and is delocalized over the Si-B-Si unit, while the geometric perturbation significantly increases its energy. Borylene (1) shows single electron transfer reactivity toward tris(pentafluorophenyl)borane (B(C₆F₅)₃), forming a frustrated radical pair [(SiNSi)B]^•+[B(C₆F₅)₃]^•-, which can be trapped by its reaction with PhSSPh, affording an ion pair [(SiNSi)BSPh][PhSB(C₆F₅)₃] (3). Remarkably, the cooperation between borylene and silylene allows the facile cleavage of the N-H bond of aniline, the P-P bond in white phosphorus, and the C═O bond in ketones and carbon dioxide, thus representing a new type of main-group element-ligand cooperativity for the activation of small molecules. In addition, 1 is a strikingly effective catalyst for carbon dioxide reduction. Computational studies reveal that the cooperation between borylene and silylene plays a key role in the catalytic chemical bond activation process.