A Hafnium-based Metal-Organic Framework as an Efficient and Multi-functional Catalyst for Facile CO₂ Fixation and Regioselective Epoxide Activations

Beyzavi, M. H.; Klet, R. C.; Tussupbayev, S.; Borycz, J.; Vermeulen, N. A.; Cramer, C. J.; Stoddart, J. F.; Hupp, J. T.; Farha, O. K.
J. Am. Chem. Soc. 2014, 136, 15861 (doi:10.1021/ja508626n).

Porous heterogeneous catalysts play a pivotal role in chemical industry. Herein, a new Hf-based MOF (Hf-NU-1000) incorporating Hf₆ clusters is reported. It demonstrates high catalytic efficiency for the activation of epoxides, facilitating the quantitative chemical fixation of CO₂ into five-membered cyclic carbonates under ambient conditions, rendering this material an excellent catalyst. As a multi-functional catalyst, Hf-NU-1000 is also efficient for other epoxide activations, leading to the regioselective and enantioretentive formation of 1,2-bifuctionalized systems via solvolytic nucleophilic ring opening.