Structurally Constrained Stibenium: Metallomimetic C−Si Bond Activation

Abstract

ABSTRACT The chemistry of structurally constrained pnictogen centers continues to attract interest within the field of metallomimetic main‐group catalysis. Herein, we report a structurally constrained stibenium cation [ 1 ] + supported by a 2,6‐bis(o‐carborano)pyridine pincer‐type ligand. This unique Sb‐based cation exhibits an unprecedented ability to activate the Si−C bonds via oxidative addition not only in hydrosilanes but also in otherwise unreactive tetraalkylsilanes. This remarkable reactivity of [ 1 ] + enables its application as a catalyst for silane redistribution under mild conditions. Experimental and density functional theory (DFT) mechanistic studies of this catalysis suggest that [ 1 ] + operates in a metallomimetic fashion, involving key steps commonly associated with transition‐metal catalysis.