Potential of Molecular Catalysts with Electron-Rich Transition Metal Centers for Addressing Long-Standing Chemistry Enigmas.

Abstract

Molecular complexes with electron-rich metal centers are highlighted as potential catalysts for the following five important chemical transformations: selective conversion of methane to methanol, capture and utilization of carbon dioxide, fixation of molecular nitrogen, water splitting, and recycling of perfluorochemicals. Our initial focus lies on negatively charged metal centers and ligands that can stabilize anionic metal atoms. Catalysts with electron-rich metal atoms (CERMAs) can sustain catalytic cycles with a "ping-pong" mechanism, where one or more electrons are transferred from the metal center to the substrate and back. The donated electrons can activate the chemical bonds of the substrate by populating its antibonding orbitals. At the last step of the catalytic cycle, the electrons return to the metal and the product interacts only weakly with the formed anion, which enables the solvent molecules to remove the product fast from the catalytic cycle and prevent subsequent unfavorable reactions. This process resembles electrocatalysis, but the metal serves as both an anode and a cathode (molecular electrocatalysis). We also analyze the usage of CERMAs as the base of Frustrated Lewis pairs proposing a new type of bimetallic catalysts. This Featured Article aspires to initiate systematic experimental and theoretical studies on CERMAs and their reactivity, the potential of which has probably been underestimated in the literature.