In Situ Formation of B═O Bond in Oxidative Dehydrogenation of Propane and as a Hunter for Alkoxyl Radicals: A Computational Study

B═O multiple bonds are fundamentally important owing to the unique property of B and its potential as a tool in catalysis. Herein by means of DFT calculations, we investigated the in situ generation of transient -B═O species in the nonmetallic inorganic boron oxides and demonstrated its superior ability to capture alkoxyl radicals under the conditions of oxidative dehydrogenation of propane (ODHP). Boron-containing materials are emerging as promising catalysts for ODHP, while an extensive understanding of the underlying mechanisms remains challenging. Through systematic mechanistic and characterization calculations, we show the feasibility for the presence of -B═O species under ODHP conditions and propose that its π nature dictates its inertness in the C-H activation of propane (Δ<i>G</i>^⧧ = 57 kcal/mol) but offers its strong ability in capturing alkoxyl radicals (barrierless with Δ<i>G</i> = -30 kcal/mol), which can then transform to the ·C₃H₆OH radical. This explains the observation of enol in the experimental study. This specific behavior of the -B═O species makes it one of the key players in the complex reaction network of ODHP and also implicates the rational design of scavengers for reactive oxygen species (ROS) and other active oxygenated species.