Single-site Organozirconium Polymerization Catalyst Embedded in a Metal–Organic Framework

Klet, R. C.; Tussupbayev, S.; Borycz, J.; Gallagher, J. R.; Stalzer, M. M.; Miller, J. T.; Gagliardi, L.; Hupp, J. T.; Marks, T. J.; Cramer, C. J.; Delferro, M.; Farha, O. K.
J. Am Chem. Soc. 2015, 137, 15680 (doi:10.1021/jacs.5b11350).

A structurally well-defined mesoporous Hf-based metal–organic framework (Hf-NU-1000) is employed as a well-defined scaffold for a highly electrophilic single-site d⁰ Zr–benzyl catalytic center. This new material Hf-NU-1000-ZrBn is fully characterized by a variety of spectroscopic techniques and DFT computation. Hf-NU-1000-ZrBn is found to be a promising single-component catalyst (i.e., not requiring a catalyst/activator) for ethylene and stereoregular 1-hexene polymerization.