Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c00481"[EN] Three metal-organic frameworks with the general formula Co(BPZX) (BPZX(2-) = 3-X-4,4'-bipyrazolate, X = H, NH2, NO2) constructed with ligands having different functional groups on the same skeleton have been employed as heterogeneous catalysts for aerobic liquid-phase oxidation of cumene with O-2 as oxidant. O-2 adsorption isotherms collected at p(O2) = 1 atm and T = 195 and 273 K have cast light on the relative affinity of these catalysts for dioxygen. The highest gas uptake at 195 K is found for Co(BPZ) (3.2 mmol/g (10.1 wt % O-2)), in line with its highest BET specific surface area (926 m(2)/g) in comparison with those of Co(BPZNH(2)) (317 m(2)/g) and Co(BPZNO(2)) (645 m(2)/g). The O-2 isosteric heat of adsorption (Q(2)) trend follows the order Co(BPZ) > Co(BPZNH(2)) > Co(BPZNO(2)). Interestingly, the selectivity in the cumene oxidation products was found to be dependent on the tag present in the catalyst linker: while cumene hydroperoxide (CHP) is the main product obtained with Co(BPZ) (84% selectivity to CHP after 7 h, p(O2) = 4 bar, and T = 363 K), further oxidation to 2-phenyl-2-propanol (PP) is observed in the presence of Co(BPZNH(2)) as the catalyst (69% selectivity to PP under the same experimental conditions).S.G., R.V., and M.M. acknowledge Universita dell'Insubria for partial funding. G.G. thanks the Italian MIUR through the PRIN 2017 Project Multi-e: Multielectron Transfer for the Conversion of Small Molecules: an Enabling Technology for the Chemical Use of Renewable Energy (20179337R7) for financial support. G.G. thanks the TRAINER project (Catalysts for Transition to Renewable Energy Future) ref. ANR-17-MPGA-0017 for support. C.P. thanks the University of Camerino and the Italian MIUR throughout the PRIN 2015 Project Towards a Sustainable Chemistry (20154 x 9ATP_002). This project has also received funding from the European Union's Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No. 641887 (project acronym: DEFNET) and the Spanish Government through projects MAT2017-82288-C2-1-P and Severo Ochoa (SEV-2016-0683). Professor Norberto Masciocchi (University of Insubria, Como, Italy) is acknowledged for fruitful discussions. The authors are also grateful to Dr. Giulia Tuci (CNR-ICCOM Florence, Italy) for help with the XPS curve fitting. The Microscopy Service of the Universitat Politècnica de València is gratefully acknowledged for the electron microscopy measurements.Nowacka, AE.; Vismara, R.; Mercuri, G.; Moroni, M.; Palomino Roca, M.; Domasevitch, K.; Di Nicola, C.... (2020). Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity. Inorganic Chemistry. 59(12):8161-8172. https://doi.org/10.1021/acs.inorgchem.0c00481816181725912Fortuin, J. P., & Waterman, H. I. (1953). Production of phenol from cumene. Chemical Engineering Science, 2(4), 182-192. doi:10.1016/0009-2509(53)80040-0Luyben, W. L. (2009). Design and Control of the Cumene Process. Industrial & Engineering Chemistry Research, 49(2), 719-734. doi:10.1021/ie9011535Matsui, S., & Fujita, T. (2001). New cumene-oxidation systems. 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