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[CuII(ttb)(H2O)3]2[CuII(ttb)Cl]2[PW12O40]·4H2O (1) (Httb = 1-(tetrazol-5-yl)-4-(triazol-1-yl)benzene) and [ClCu6I(trz)4][ClCu5I(trz)4]2[CuII(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···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.