Heterogeneous derivatives of catalysts discovered by Ziegler and Natta are important for the industrial production of polyolefin plastics. However, the interaction between precatalysts, alkylaluminum activators, and oxide supports to form catalytically active materials is poorly understood. This is in contrast to homogeneous or model heterogeneous catalysts that contain resolved molecular structures that relate to activity and selectivity in polymerization reactions. This study describes the reactivity of triisobutylaluminum with high surface area aluminum oxide and a zirconocene precatalyst. Triisobutylaluminum reacts with the zirconocene precatalyst to form hydrides and passivates -OH sites on the alumina surface. The combination of passivated alumina and zirconium hydrides formed in this mixture generates ion pairs that polymerize ethylene.

Lutidine-derived bis-N-heterocyclic carbene (NHC) ruthenium CNC-pincer complexes (Ru-CNC's) were prepared. Depending on the synthetic procedure, normal (1, 2) or mixed normal/abnormal NHC-complexes (3) are formed. In the presence of phosphazene base, Ru-CNC complexes activate nitriles to give ketimino compounds 4-6. Nitrile adduct 4 shows reactivity toward strong bases to yield dearomatized complex 7, which heterolytically activates H₂ to form the bis-hydrido complex 8. Finally, these Ru-CNC's are active in catalytic hydrogenation of CO₂ to formate salts, and unlike the phosphine-containing Ru-PNP counterpart, they also catalyze the selective hydrogenation of esters to alcohols.

The metal-ligand cooperative activation of CO₂ with pyridine-based ruthenium PNP pincer catalysts leads to pronounced inhibition of the activity in the catalytic CO₂ hydrogenation to formic acid. The addition of water restores catalytic performance by activating alternative reaction pathways and leads to unprecedented Ru-catalyzed CO₂ hydrogenation activity. The mechanism of the underlying chemical transformations is proposed on the basis of DFT calculations, kinetic experiments, and NMR reactivity studies.