Aerobic Epoxidation of Olefins Catalyzed by the Cobalt‐Based Metal–Organic Framework STA‐12(Co)

Beier, Matthias; Kleist, Wolfgang; Wharmby, Michael T.; Kissner, Reinhard; Kimmerle, Bertram; Wright, Paul A.; Grunwaldt, Jan‐Dierk; Baiker, Alfons

doi:10.1002/chem.201101223

Cited by 117 publications

(63 citation statements)

References 60 publications

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“…As mentioned earlier, these species will afterwards transfer the oxygen to the olefin, resulting in the epoxide product. The catalytic evaluation of Co-STA-12 resulted in the formation of the epoxide with an excellent selectivity of 90%, which was in agreement with the proposed mechanism 93 .…”

Section: Co-based Mofssupporting

confidence: 86%

“…In a second step, the acylperoxy radical is able to follow 2 possible pathways, it can either react with the olefin to produce the epoxide, or with the Co-ZIF to form Co-peroxy species, which on their turn can transfer an oxygen atom directly to the olefins. In a report of Beier et al 93 , pure O 2 was applied as an oxidant with DMF as a solvent (entry 9 Table 4). …”

Section: Co-based Mofsmentioning

confidence: 99%

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Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

2014

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Since the discovery of Metal Organic Frameworks (MOFs) in the early 1990, the amount of new structures has grown exponentially. A MOF typically consists of inorganic nodes that are connected by organic linkers to form crystalline, highly porous structures. MOFs have attracted a lot of attention lately, as the versatile design of such materials holds promises of interesting applications in various fields. In this review, we will focus on the use of MOFs as heterogeneous oxidation catalysts. MOFs are very promising candidates to replace homogeneous catalysts by sustainable and stable heterogeneous catalysts. The catalytic active function can be either the active metal sites of the MOF itself or can be introduced as an extra functionality in the linker, a dopant or a "ship-in-a-bottle" complex. As the pore size, pore shape and functionality of MOFs can be designed in numerous ways, shape selectivity and even chiral selectivity can be created. In this review, we will present an overview on the state of the art of the use of MOFs as a heterogeneous catalyst in liquid phase oxidation reactions.

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Section: Co-based Mofssupporting

confidence: 86%

Section: Co-based Mofsmentioning

confidence: 99%

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

2014

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“…[40] Furthermore, the oxidative dehydration of N-methylformamide has been previously reported using supported metals. [41] Methyl isocyanide undergoes isomerization to methyl cyanide (acetonitrile) in the last step, a reaction that has been previously promoted under heat [42] or catalyzed by metal complexes. [43] The generation of mesoporosity in zeolites has been generally at to improving accessibility and/or diffusional constraints inherent in microporous zeolites.…”

mentioning

confidence: 99%

Hierarchical Zeolites and their Catalytic Performance in Selective Oxidative Processes

et al. 2015

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Hierarchical ZSM-5 zeolites prepared using a simple alkali treatment and subsequent HCl washing are found to exhibit unprecedented catalytic activities in selective oxidation of benzyl alcohol under microwave irradiation. The metal-free zeolites promote the microwave-assisted oxidation of benzyl alcohol with hydrogen peroxide in yields ranging from 45-35 % after 5 min of reaction under mild reaction conditions as well as the epoxidation of cyclohexene to valuable products (40-60 % conversion). The hierarchically porous systems also exhibited an interesting catalytic activity in the dehydration of N,N-dimethylformamide (25-30 % conversion), representing the first example of transition-metal free catalysts in this reaction.

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“…So far, a variety of new catalysts has been developed in the past decades to achieve the efficient transformation from alkenes into epoxides including both homogeneous catalysts (ruthenium porphyrin, manganese complexes, iron complexes, etc Mn III –polymer catalysts, MOFs, etc …”

Section: Introductionmentioning

confidence: 99%

Amino‐Induced 2D Cu‐Based Metal–Organic Framework as an Efficient Heterogeneous Catalyst for Aerobic Oxidation of Olefins

Tang

Cai

Xie

et al. 2020

Chemistry A European J

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With the assistance of hydrogen bonds of the o‐amino group, we have successfully tuned a coordination structure from a metal–organic polyhedron (MOP) to a two‐dimensional (2D) metal–organic framework (MOF). The amino group forms hydrogen bonds with the two vicinal carboxylic groups, and induces the ligand to coordinate with copper ions to form the 2D structure. The obtained 2D Cu‐based MOF (Cu‐AIA) has been applied as an efficient heterogeneous catalyst in the aerobic epoxidation of olefins by using air as oxygen source. Without the aggregation problem of active sites in MOPs, Cu‐AIA possesses much higher reactivity than MOP‐1. Furthermore, the amino group of the framework has been used as a modifiable site through post‐synthetic metalation (PSMet) to prepare a 2D MOF‐supported Pd single‐site heterogeneous catalyst, which shows excellent catalytic performance for the Suzuki reaction. It indicates that Cu‐AIA can also work as a good 2D MOF carrier for the derivation of other heterogeneous catalysts.

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Aerobic Epoxidation of Olefins Catalyzed by the Cobalt‐Based Metal–Organic Framework STA‐12(Co)

Cited by 117 publications

References 60 publications

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

Hierarchical Zeolites and their Catalytic Performance in Selective Oxidative Processes

Amino‐Induced 2D Cu‐Based Metal–Organic Framework as an Efficient Heterogeneous Catalyst for Aerobic Oxidation of Olefins

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