Sub-nano clusters are promising catalysts due to their high atom utility, and ability to outperform bulk-like catalysts by breaking scaling relations. Pure Pt clusters have been studied as alkane dehydrogenation catalysts, as have various dopants to improve catalyst selectivity, including B, Si, 8 Ge 7 Sn, and S. Surface-supported clusters are fluxional, isomerizing rapidly under the high temperatures of real reactions such that metastable structures are thermally populated. Higher-energy isomers often show greater catalytic activity than the global minimum isomer. If the kinetic barriers for isomerisation are low, then the isomer populations will be determined by a Boltzmann distribution. If a cluster were to have high isomerisation barriers then the ensemble would not thermally equilibrate, and macroscopic properties would be determined by the reduced set of accessible isomers, which could be useful if the prevalent isomers have superior activity. Our most recent work focused on Al 2 O 3 -supported PtGe subnanoclusters, which were pre-pared experimentally after Ge was theoretically predicted to be a suitable dopant. We found that not only were the prepared Pt 4 Ge clusters reasonably stable and selective, but that they slowly converted to a partially-coked form, Pt 4 GeC 2 , which was stable against further coking. This parallels the behavior of PtSn nanoparticles which remain active and stable despite building up more coke than their pure Pt analogues. Transforming a poisoning process into in-situ catalyst synthesis by doping, illustrated in the right-most part of Figure is a powerful new strategy in catalyst design. To apply this strategy to other reactions, we must first understand the fundamental chemistry behind the efficacy of Pt 4 GeC 2 .