Zirconium-Catalyzed C–H Alumination of Polyolefins, Paraffins, and Methane
Uddhav Kanbur, Alexander L. Paterson, Jéssica Rodríguez, Andrew L. Kocen, Ryan Yappert, Ryan A. Hackler, Yiyu Wang, Baron Peters, Massimiliano Delferro, Anne M. LaPointe, Geoffrey W. Coates, Frédéric A. Perras, Aaron D. Sadow
Abstract
High Resolution Image Download MS PowerPoint Slide C–H/Et-Al exchange in zirconium-catalyzed reactions of saturated hydrocarbons and AlEt 3 affords versatile organoaluminum compounds and ethane. The grafting of commercially available Zr(O t Bu) 4 on silica/alumina gives monopodal ≡SiO–Zr(O t Bu) 3 surface pre-catalyst sites that are activated in situ by ligand exchange with AlEt 3 . The catalytic C–H alumination of dodecane at 150 °C followed by quenching in air affords n -dodecanol as the major product, revealing selectivity for methyl group activation. Shorter hydrocarbon or alcohol products were not detected under these conditions. Catalytic reactions of cyclooctane and AlEt 3, however, afford ring-opened products, indicating that C–C bond cleavage occurs readily in methyl group-free reactants. This selectivity for methyl group alumination enables the C–H alumination of polyethylenes, polypropylene, polystyrene, and poly-α-olefin oils without significant chain deconstruction. In addition, the smallest hydrocarbon, methane, undergoes selective mono-alumination under solvent-free catalytic conditions, providing a direct route to Al–Me species.