Ligand Based C-H Bond Weakening for Synthesis and Electrocatalysis with Earth-Abundant Metals
The selective, efficient, and sustainable activation of carbon-hydrogen bonds continues to be a critical area of research. Current synthetic methodologies heavily rely on transition metal catalysts to mediate the reactivity of C-H bonds for making medicines, fuels, agrochemicals, and materials. We are broadly interested in leveraging C-H bonds housed within chelating ligand frameworks to move around protons (H+), hydrides (H-) and hydrogen atoms (H•). We have discovered that an amine-rich cyclopentadienyl ligand (CpN3) coordinated to iron facilitates electrocatalytic H2 production in the presence of exogenous acid. While coordination chemists often consider Cp ligands as unreactive “spectator” ligands, H2 production involves a stereoselective endo-CpN3 protonation step followed by ligand-to-metal proton transfer – making the CpN3 ligand chemically noninnocent. In a separate endeavor, we aim to understand the magnitude of C-H bond weakening when an alkane moiety interacts with a transition metal (i.e., agostic interactions). To study the C-H bond strength properties, we use diamondoid pincer ligands coordinated to Ni and Pd, which provide unique insights into the thermochemical requirements for C-H activation with unactivated alkanes.
Hosted by Professor Alan Goldman