Catalytic Nitrous Oxide Degradation with Group 15 Clusters

Nitrous oxide (N₂O) is sometimes referred to as the forgotten greenhouse gas, but ignoring it would be a mistake. N₂O has a greenhouse warming potential 300× that of CO₂ and anthropogenic emissions are increasing. Yet, compared to CO₂, homogeneous catalysts that mediate its reduction are scarce. We present a range of cluster catalysts based on abundant and inexpensive p-block elements that mediate the conversion of N₂O to environmentally benign N₂. The catalysts studied offer many critical advantages, and systems can be tuned for performance, recyclability, selectivity, air stability, or commercial availability. Pnictogen clusters present themselves as a general platform in N₂O reduction chemistry, and control reactions confirm that these clusters offer access to reactivity that simple mono-pnictogen molecules do not. Mechanistic investigations reveal that the low-valent clusters can access a –1/+1 redox couple which goes beyond classical main group redox couples, and will unlock a vault of hitherto unknown chemical space.