Bifunctional Metal–Organic Layers for Tandem Catalytic Transformations Using Molecular Oxygen and Carbon Dioxide
Wenjie Shi, Yangjian Quan, Guangxu Lan, Kaiyuan Ni, Yang Song, Xiaomin Jiang, Cheng Wang, Wenbin Lin
Abstract
Tandem catalytic reactions improve atom- and step-economy over traditional synthesis but are limited by the incompatibility of the required catalysts. Herein, we report the design of bifunctional metal–organic layers (MOLs), HfOTf-Fe and HfOTf-Mn, consisting of triflate (OTf)-capped Hf6 secondary building units (SBUs) as strong Lewis acidic centers and metalated TPY ligands as metal active sites for tandem catalytic transformations using O2 and CO2 as coreactants. HfOTf-Fe effectively transforms hydrocarbons into cyanohydrins via tandem oxidation with O2 and silylcyanation whereas HfOTf-Mn converts styrenes into styrene carbonates via tandem epoxidation and CO2 insertion. Density functional theory calculations revealed the involvement of a high-spin FeIV (S = 2) center in the challenging oxidation of the sp3 C–H bond. This work highlights the potential of MOLs as a tunable platform to incorporate multiple catalysts for tandem transformations.