Cooperative bimetallic reactivity: hydrogen activation in two-electron mixed-valence compounds

Reversible dihydrogen uptake by a two-electron mixed-valence di-iridium complex is examined with nonlocal density-functional calculations. Optimized metrics compare favorably with crystal structures of isolated species, and the calculated activation enthalpy of acetonitrile exchange is accurate within experimental error. Dihydrogen attacks the Ir(2) core at Ir(II); the Ir(0) center is electronically saturated and of incorrect orbital parity to interact with H(2). Isomeric eta(2)-H(2) complexes have been located, and harmonic frequency calculations confirm these to be potential energy minima. A transition state links one such complex with the final dihydride; calculated atomic charges suggest a heterolytic H(2) bond scission within the di-iridium coordination sphere. This investigation also establishes a ligand-design criterion for attaining cooperative bimetallic reactivity, namely, that the supporting ligand framework has sufficient mechanical flexibility so that the target complex can accommodate the nuclear reorganizations that accompany substrate activation.