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, and 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 monopnictogen
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.