Highly efficient multi-site synergistic catalysis of a polyoxovanadate-based metal–organic framework for benzylic C–H bond oxidation

Abstract

The selective oxidation of C-H bonds of benzylic compounds to synthesize high-value-added ketones remains a challenge under mild conditions, and the ambiguity of its oxidation mechanism limits the further development...

Recent advances in oxidative catalytic applications of polyoxovanadate-based inorganic–organic hybrids

“…9a). 51 Given its high catalytic activity in the oxidative conversion of benzylalkanes (conv. of all substrates >96%), the mechanism was further investigated through a series of validation experiments along with DFT calculations.…”

Experimental and Theoretical Studies on Two Dual-Functional Organic–Inorganic Hybrids Based on [V4O12]4– Clusters

“…The structure of {V x O y } n − ranges from a simple [VO 4 ] 3– tetrahedron to polymerization units ([V 2 O 7 ] 4– , [V 3 O 9 ] 3– , [V 4 O 12 ] 4– , [V 6 O 18 ] 6– , and [V 10 O 28 ] 6– ) owing to different VO n ( n = 4, 5, 6) polyhedral fragments. The negatively charged tetravanadate [V 4 O 12 ] 4– cluster is one of the important inorganic building units among POVs. − For instance, Zur Loye and co-workers synthesized a 3D material based on [V 4 O 12 ] 4– and Co-organic complex with a concomitant reversible structure change; Luo and co-workers made a lilac–shaped photocatalytic material modified with {Ag 7 } 7+ and [V 4 O 12 ] 4– clusters; Hu and co-workers reported a double-anion catalyst stemmed from bicapped [PNb 12 O 40 (VO) 2 ] and tetranuclear [V 4 O 12 ] 4– for rapid transformation of chemical warfare agents; Liu et al constructed a [V 4 O 12 ] 4– -based metal–organic framework (MOF) with multiple active sites to catalyze benzylic C–H bond oxidation; Aureliano et al summarized various types of iso-POVs including cyclic tetravanadate (V 4 ) interaction with proteins in solution, which can affect various biological processes …”

“…The structure of {V 4− cluster is one of the important inorganic building units among POVs. 33−37 For instance, Zur Loye and co-workers synthesized a 3D material based on [V 4 O 12 ] 4− and Co-organic complex with a concomitant reversible structure change; 38 Luo and co-workers made a lilac−shaped photocatalytic material modified with {Ag 7 } 7+ and [V 4 O 12 ] 4− clusters; 39 Hu and co-workers reported a double-anion catalyst stemmed from bicapped [PNb 12 O 40 (VO) 2 ] and tetranuclear [V 4 O 12 ] 4− for rapid transformation of chemical warfare agents; 40 − -based metal−organic framework (MOF) with multiple active sites to catalyze benzylic C−H bond oxidation; 41 Aureliano et al summarized various types of iso-POVs including cyclic tetravanadate (V 4 ) interaction with proteins in solution, which can affect various biological processes. 42 Furthermore, copper−organic complexes with novel structure have widespread application in chiral materials, 43 photology, 44 catalysts, 45,46 gas absorption, 47 and so on.…”

A Metal‐Organic Complex Constructed from Co(II), Azo‐amide‐pyridyl and Benzenetricarboxylate Mixed Ligands: Efficient Catalysis for Selective Oxidation of Benzyl Alcohols to Benzyl Acids

“…Metal-organic complexes (MOCs) consist of periodically connected metal nodes and organic ligands, [18] which have become one of the most popular heterogeneous catalysts, especially in various catalytic oxidation processes, due to their structural diversity, functional adaptability. [19][20][21] Additionally, metal centers in MOCs are generally considered to be catalytic active sites in these oxidation processes to promote the reaction process.…”