Synthesis, Characterization, and Heterogeneous Catalytic Implementation of Sulfated Alumina Nanoparticles. Arene Hydrogenation and Olefin Polymerization Properties of Supported Organozirconium Complexes

摘要

Sulfated alumina nanoparticles (n-AlS) have been prepared as a highsurface- area support/activator for organozirconium catalysts. The large external surface area allows chemisorption of ca. 3 times more organozirconium catalyst per square nanometer than previously possible on bulk sulfated alumina. It is found that Cp*ZrMe2-AlS (Cp* = η5-(CH3)5C5, Me = CH3) and ZrBz3-AlS (Bz = CH2C6H5) are active catalysts for arene hydrogenation as well as for olefin polymerizations. The less sterically encumbered ZrBz3-AlS exhibits higher polymerization activity and a greater arene hydrogenation turnover frequency than the slightly more encumbered Cp*ZrMe2-AlS. Catalyst ZrBz3-AlS also displays a larger tolerance for sterically demanding hydrogenation substrates as well as increased 1-hexene incorporation in ethylene/1-hexene copolymerizations.