Highly Efficient Synthesis of p-Benzoquinones Catalyzed by Robust Two-Dimensional POM-Based Coordination Polymers

Selective oxidation of alkyl-substituted phenols offers efficient access to p-benzoquinones (BQs) that serve as key components for synthesizing biologically active compounds, but rational manufacture of efficient recyclable catalysts for such a reaction remains a severe challenge. Herein, two crystalline 2D polyoxometalate-based coordination polymers (POMCPs), formulated as H₃[Cu^I₃(L)₃]₂[PM₁₂O₄₀]·xH₂O (M = Mo, x = 4 for 1; M = W, x = 6 for 2; and HL = 4-(1H-tetazol-5-yl)pyridine), are prepared by a mineralizer-assisted one-step synthesis strategy and explored as heterogeneous catalysts for p-BQs synthesis. Both compounds have been characterized through elemental analysis, EDS analysis, infrared spectroscopy, UV-vis diffuse reflectance spectrum, EPR, XPS, BET, single-crystal, and powder X-ray diffraction. Single-crystal X-ray diffraction analysis indicates that both 1 and 2 exhibit an interesting 2D sheet structure composed of 2-connected Keggin type anions [PM₁₂O₄₀]^3- and hexa-nuclear {Cu^I₆(HL)₆} cluster-based metal-organic chains via Cu···O interactions. When used as catalysts, POMCPs 1 and 2 have excellent catalytic activities in the selective oxidation of substituted phenols to p-BQs with H₂O₂. Notedly, in the model reaction from 2,3,6-trimethylphenol (TMP) to the vitamin E key intermediate trimethyl-p-benzoquinone (TMBQ), the catalytic activities expressed by turnover frequency (TOF) of 1 and 2 can reach an unprecedented 2400 and 2000 h^-1, respectively, at close to 100% TMBQ yield. The truly heterogeneous nature, stability, and structural integrity of both catalysts were ascertained by FTIR, PXRD techniques, and the following cycles. Mechanism studies reveal that both catalysts can involve a dual reaction pathway through a heterolytic oxygen atom transfer mechanism and homolytic radical mechanism. Moreover, the 2D POMCPs with highly accessible bilateral active sites and efficient mass transfer efficiency possess superior catalytic performance to their analogous 3D species.