Improving Catalyst Activity in Hydrocarbon Functionalization by Remote Pyrene-Graphene Stacking.

A copper complex bearing an N-heterocyclic carbene ligand with a pyrene "tail" attached to the backbone has been prepared and supported on reduced graphene oxide (rGO). The free and supported copper materials have been employed as homogeneous and heterogeneous catalysts in the functionalization of hydrocarbons such as n-hexane, cyclohexane, and benzene through incorporation of the CHCO2 Et unit from ethyl diazoacetate. The graphene-anchored complex displays higher reaction rates and induces higher yields than its soluble counterpart, features that can be rationalized in terms of a decrease in electron density at the metal center due to a remote net electronic flux from the supported copper complex to the graphene surface.

Methane functionalization in water with micellar catalysis.

The functionalization of methane in water as the reaction medium (where it is nearly insoluble) at room temperature using micellar catalysis is described. Aggregates are formed from surfactant molecules and act as methane concentrators, also trapping the catalyst (a silver-based complex) and the diazo reagent (ethyl diazoacetate, EDA), providing yields of ethyl propionate up to 14% (referred to as EDA). This is the first example of methane being functionalized in water at room temperature.