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Published on: May 12, 2023
Polyoxometalate Catalysis under Alkaline Conditions: Self-Assembly of Lanthanum Ion-Doped Steady
Mei-Qian Fu1, Yu Xiong1, Wei-Dong Yu2
1College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410000, China.
Abstract:
The convenient and effective catalytic synthesis of quinazolines holds considerable significance due to their high economic value, and designing a cluster-type alkali-resisting catalyst such as polyoxometalates (POMs) still poses a significant challenge. Herein, three lanthanum ion-doped steady polyoxophosphitemolybdates with the formulas of [CH3NH3]6{La(H2O)3Na[Mo6O12(OH)3(HPO3)4]2}·10H2O (1), [CH3NH3]2{La(H2O)[Mo6O12(OH)3(HPO3)4]}·8H2O (2), and [CH3NH3]5{La2(H2O)8Na[Mo6O12(OH)3(HPO3)3 (PO4)]2}·16H2O (3) were synthesized by using HPO32- as the template. Structural analysis revealed that 1 forms a three-dimensional structure through the connection of La3+ with an hourglass-shaped {Na[P4Mo6O27]2} unit. 2 forms a three-dimensional structure with a porous channel and the same {P4Mo6O27} building block. When the synthetic microenvironment was adjusted by changing the type of reducing agent, some of the hypophosphite in the building units was oxidized, thereby altering the structure, and compound 3 was formed. All compounds are alkali-resistant and catalytically active toward the conversion of 2-aminobenzyl alcohol and benzonitrile into 2-phenylquinazoline, and 2 achieves the best yield of 91.7%, which is much better than those of classic Keggin {PMo12} and inorganic CaMoO4, indicating the synergistic catalytic effect of Mo and La centers. Also, compound 2 exhibits good activity and reliability in catalyzing reactions of the same type with different substrates.
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