Hydrocarbon Functionalization in Porous Materials

Hydrocarbons are cheap and abundant feedstocks readily derived from both fossil fuels and emerging renewable resources. Despite their abundance, hydrocarbons have limited applications in chemical synthesis due to the inertness of C–H bonds towards both homolytic and heterolytic bond cleavage. I will share two very different approaches to the selective functionalization of simple hydrocarbons that address these challenges. First, I will highlight a bio-inspired approach to achieve selective alkane hydroxylation using iron-based metal–organic frameworks. The critical influence of both primary and secondary coordination sphere elements on catalyst reactivity, selectivity, and stability will be detailed. Second, I will describe the identification and characterization of a simple heterogeneous base catalyst that converts aromatic hydrocarbons, CO2, and methanol into the corresponding aromatic esters at elevated temperatures. The transformation occurs via a two-step, semi-continuous cycle, and represents the first hydrocarbon CO2 insertion process that does not consume any energy-intensive stoichiometric reagents.






Dianne Xiao, PhD (Stanford University)