Multiunit Catalysts with Synergistic Reactivity: Three-Dimensional Polyoxometalate-Based Coordination Polymers for Highly Efficient Synthesis of Functionalized p-Benzoquinones

The rational design of highly efficient catalysts for the synthesis of functionalized p-benzoquinones (p-BQs) is of great significance for the manufacture of bioactive compounds. Herein, two 3D crystalline polyoxometalate-based coordination polymers (POMCPs) are used as heterogeneous catalysts for the synthesis of p-BQs, which are H[Cu-II(ttb)(H2O)(3)](2)[Cu-II(ttb)Cl](2)[PW12O40]center dot 4H(2)O (1) (Httb = 1-(tetrazol-S-yl)-4-(triazol-1-yl)benzene) and [ClCu6I(trz)(4)] [ClCu5I(trz)(4)](2)[Cu-II(H2O)][PW12O40] (2) (trz = 1,2,4-triazole). Both compounds were characterized by elemental analysis, IR, XPS, solid diffuse reflective spectroscopy, TG analysis, and single-crystal X-ray diffraction. In 1, Keggin anions [PW12O40](3-) locate in 1D square channels constructed from wave-like Cu-ttb layers to form a 3D POMCP by coordinating to Cu ions, and in 2, [PW12O40](3-) anions situate in eight-membered Cu-trz channels via Cu center dot center dot center dot O interactions to yield a 3D POMCP structure. The catalytic activities of 1 and 2 have been evaluated in the selective oxidation of alkylphenols/alkoxybenzenes/methylnaphthalene, especially in the oxidation reaction of 2,3,6-trimethylphenol (TMP) to 2,3,5-trimethyl-p-benzoquinone (TMBQ vitamin E key intermediate), with H2O2 as oxidant. By using catalysts 1 and 2 under optimal conditions, the yield of TMBQ can reach 99% and 96% within 10-20 min, respectively. Both catalysts demonstrated high turnover frequencies (300 h(-1) for 1 and 600 h(-1) for 2) and the truly heterogeneous nature. 1 and 2 catalyzed the synthesis of p-BQs on the basis of effective cooperative catalytic activities by POMs and metal nodes.