Additive-free selective oxidation of aromatic alcohols with molecular oxygen catalyzed by a mixed-valence polyoxovanadate-based metalorganic framework

Tian, Hongrui1,2; Li, Runhan3; Miao, Jun1,2; Liu, Shuxia4; Wang, Fengfeng5; Zheng, Zhiping1,2

2023-07-04

10.1039/d3dt01403g

DALTON TRANSACTIONS   影响因子和分区

1477-9226

1477-9234

Selective oxidation of alcohols to aldehydes is an industrially significant chemical transformation. Herein, we report a mixed-valence polyoxovanadate-based metal-organic framework (MOF), (H(2)bix)(5){[Cd(bix)(2)][(V8V7O36Cl)-V-IV-O-V](2)}center dot 3H(2)O (V-Cd-MOF), for catalyzing the additive-free oxidation of a series of aromatic alcohols with high selectivity and in nearly quantitative yield to the corresponding aldehydes with O-2 as the oxidant. Experimental results, corroborated with density functional theory calculations, indicate that it is the synergistic operation of the dual active sites of the V-IV-O-V-V building units in the polyoxovanadate cluster that is responsible for the excellent catalytic performance observed: on the one hand, the exposed and readily accessible reduced V-IV site is believed to activate O-2, resulting in a reactive oxygen species for the subsequent activation and breaking of the substrate's C-alpha-H bond. On the other hand, the V-V site coordinates with the alcoholic O atom to facilitate the cleavage of the O-H bond. The catalyst can be recycled by centrifugation and re-used at least five times with uncompromised performance. To our knowledge, V-Cd-MOF represents the first example of a polyoxometalate-based MOF catalyst for additive-free selective oxidation of alcohol to aldehyde with O-2 as an oxidant.

SCI ; EI

英语

第一 ; 通讯

Stable Support Plan Program of Shenzhen Natural Science Fund[20200925161141006] ; Shenzhen Nobel Prize Scientists Laboratory Project (Shenzhen Grubss Institute)[C17783101] ; National Natural Science Foundation of China["92261203","22201123","21971106","22172022","22101118"] ; Shenzhen Fundamental Research Program[JCYJ20220530115001002]

Chemistry

Chemistry, Inorganic & Nuclear

WOS:001015562800001

ROYAL SOC CHEMISTRY

20232714355025

Additives ; Aromatic compounds ; Catalysts ; Density functional theory ; Molecular oxygen ; Organic polymers ; Organometallics ; Oxidants ; Oxidation

Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Inorganic Compounds:804.2 ; Organic Polymers:815.1.1 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Guangdong, Peoples R China
3.South China Normal Univ, Sch Chem, Guangzhou 510006, Guangdong, Peoples R China
4.Northeast Normal Univ, Coll Chem, Key Lab Polyoxometalate & Reticular Mat Chem, Minist Educ, Ren Min St 5268, Changchun 130024, Jilin, Peoples R China
5.Natl Inst Food & Drug Control, 31 Huatuo Rd, Beijing 102600, Peoples R China

Tian, Hongrui,Li, Runhan,Miao, Jun,et al. Additive-free selective oxidation of aromatic alcohols with molecular oxygen catalyzed by a mixed-valence polyoxovanadate-based metalorganic framework[J]. DALTON TRANSACTIONS,2023,52(26):9121-9130.

Tian, Hongrui,Li, Runhan,Miao, Jun,Liu, Shuxia,Wang, Fengfeng,&Zheng, Zhiping.(2023).Additive-free selective oxidation of aromatic alcohols with molecular oxygen catalyzed by a mixed-valence polyoxovanadate-based metalorganic framework.DALTON TRANSACTIONS,52(26),9121-9130.

Tian, Hongrui,et al."Additive-free selective oxidation of aromatic alcohols with molecular oxygen catalyzed by a mixed-valence polyoxovanadate-based metalorganic framework".DALTON TRANSACTIONS 52.26(2023):9121-9130.