A New Hepta-Nuclear Ti-Oxo-Cluster-Substituted Tungstoantimonate and Its Catalytic Oxidation of Thioethers

Abstract

A neoteric hepta-nuclear Ti-oxo-cluster-substituted tetrameric tungstoantimonate [H2N­(CH3)2]22Na18{Ti7O6(SbW9O33)4}2·124H2O (1) has hydrothermally been synthesized and tested by single-crystal/powder X-ray diffraction, IR spectra, and thermal analysis. The glamorous feature of this tetrameric polyoxoanion is an uncommon hepta-nuclear Ti-oxo-cluster octahedron [Ti7O6]16+ enclosed in four [B-α-SbW9O33]9– building units. As a heterogeneous catalyst, the investigation on catalytic oxidation with H2O2 for multiple thioethers indicated that 1 possesses high conversion and remarkable selectivity. Additionally, 1 exhibits good stability and excellent recyclability.

Ring-Shaped Polyoxometalate Built by {Mn 4 PW 9 } and PO 4 Units for Efficient Visible-Light-Driven Hydrogen Evolution

“…[1][2][3][4][5][6][7] The versatile lacunary POM fragments generated by removing one or more skeletal MO 6 groups can serve as multidentate O-donor inorganic ligands to construct mono-or multinuclear transition-metal-substituted polyoxometalates (TMSPs). [8][9][10][11][12][13][14][15] Currently, the design and preparation of highnuclearity TMSPs remain one of the most interesting topics in synthetic chemistry. To date, various high-nuclearity TMSPs have been made such as [H 56 Fe 28 P 8 W 48 O 248 ] 28− , 16 [{Co 4 (OH) 3 PO 4 } 4 (PW 9 O 34 ) 4 ] 28− , 17 [Cu 20 Cl(OH) 2 (H 2 O) 12 (P 8 W 48 O 184 )] 25− , 18 [H 6 Ni 20 P 4 W 34 (OH) 4 O 136 (enMe) 8 (H 2 O) 6 ] 6− , 19 [{Ni 6 (Tris)(en) 3 (BTC) 1.5 ( 11 Among categories of TMSPs, the assembly of multinuclear Mn-containing POMs (Mn-POMs) has continuously developed into one of the most intriguing research subjects considering their extraordinary performance in the field of molecular magnetism and more recently photocatalysis.…”

Single‐Molecule Magnetic, Catalytic and Photoluminescence Properties of Heterometallic 3d–4f [Ln{PZn2W10O38(H2O)2}2]11− Tungstophosphate Nanoclusters

“…Polyoxometalates can be used as catalysts due to their vital properties such as redox properties, proton‐transfer reactions, and structural variety. The polyoxometalates are widely used as catalyst for the oxidation of thioethers especially in H 2 O 2 ‐based oxidation reactions since no toxic by‐products are produced during the reaction [35] . Nowadays, much attention has recently been focused on the use of the POMs as catalysts in the oxidation reaction of organic thioether compounds for the selective syntheses of sulfoxides and sulfones which are used as synthetic intermediates in pharmaceutical field, sulfoxidation reactions, chemical industry, medicinal chemistry, and biochemistry.…”

A New Hexa‐TiIV‐Substituted Sandwich‐Type Polyoxotungstate: Hydrothermal Synthesis, Structure, and Oxidative Decontamination of Chemical Warfare Agent Simulant

“…The FT‐IR spectra characteristic vibration bands locating at 997, 953, 904, 777 and 725 cm –1 of recovered catalyst after forth‐run reaction was coincident with that of fresh 1 (Figure S5), suggesting that the sandwich‐type polyoxoanion structure of recovered catalyst was still retained. [5b], , The reason for some differences in FT‐IR spectra may be that the enMe molecules leave from recovered catalyst in the process of extraction upon completion of the reaction.…”

“…Recently, hydrothermal technique coupled with the lacunary directing synthetic strategy of lacunary sites of POM fragments has been used by our group to make TMSPs, resulting in a series of novel Ni II ‐/Cu II ‐/Mn II,III ‐/Zr IV ‐cluster substituted POMs . As our continuous and extended work, the hydrothermal synthesis of TiSPs was explored and a hepta‐Ti‐substituted antimoniotungstate, [Ti 7 O 6 (SbW 9 O 33 ) 4 ] 20– , was successfully made, which was the first example of TiSPs by hydrothermal method . Furthermore, the performance of TiSPs remain less explored.…”

“…Furthermore, the performance of TiSPs remain less explored. In spite of the literatures involving the oxidation of thioethers, [8a] and the epoxidation of alkenes[8b] based on Ti‐incorporating POMs have been reported, it is black that the degradation of chemical warfare agent (CWA) simulants in the presence of TiSPs. Hence, the catalytic decontamination of CWA simulants by TiSPs have aroused our intense attraction.…”