Electron Deficient Ir-O Bonds Promote Heterogeneous Ir-Catalyzed Anti-Markovnikov Hydroboration of Alkenes under Mild Neat Conditions.

Tuning electronic characteristics of metal-ligand bonds based on reaction pathways to achieve efficient catalytic processes has been widely studied and proven to be feasible in homogeneous catalysis, but it is scarcely investigated in heterogeneous catalysis. Herein, we demonstrate the regulation of the electronic configuration of Ir-O bonds in an Ir single-atom catalyst according to the borane activation mechanism. Ir-O bonds in Ir/Ni(OH) are found to be more electron-poor than those in Ir/NiO. Despite the mild solvent-free conditions and ambient temperature, Ir/Ni(OH) exhibits outstanding performance for the hydroboration of alkenes, furnishing the desired alkylboronic esters with a turnover frequency value of ≤3060 h and 99% anti-Markovnikov selectivity, which is significantly better than that of Ir/NiO (42 h). It is further proven that the more electron-poor Ir-O bonds as active centers are more oxidative and so benefit the activation of the H-B bond in the reductive pinacolborane.