Pyrazine-bridged molybdenum(0) carbonyl and molybdenum(VI) oxide network solids as catalysts for epoxidation and sulfoxidation

Gomes, Diana M.; Silva, Andreia F.; Gomes, Ana C.; Neves, Patrícia; Valente, Anabela A.; Gonçalves, Isabel S.; Pillinger, Martyn

doi:10.1016/j.cattod.2023.114050

“…However, the operation of the greener oxidants generally requires the use of a catalyst. Various catalysts have been explored, including metal oxides, , nanoparticles of noble metals, , metal-functionalized composite materials, − polyoxometalates, , and metal–organic frameworks (MOFs), − among which vanadate (V–O)-based ones stand out because of their high activity, ready availability, and low costs. The initial efforts in this vein concentrated on the catalytic use of V 2 O 5 , with which the oxidation of sulfides using tert -butyl hydroperoxide (TBHP), H 2 O 2 , cumene hydroperoxide, or O 2 as oxidants was achieved.…”

Section: Introductionmentioning

confidence: 99%

Modulating the Catalytic Properties of Polyoxovanadates with Transition-Metal-Complex Units for Selective Oxidation of Sulfides

Pan,

Tian,

Zheng

2024

Inorg. Chem.

0

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Selective oxidation of sulfides to sulfoxides is of great significance in the synthesis of pharmaceuticals, desulfurization of fuels, and detoxification of sulfur mustard chemical warfare agents. Designing selective catalysts to achieve the efficient transformation of sulfides to sulfoxides is thus highly desired. Herein, we report three transition metal-complex-functionalized polyoxovanadates,(3) (BPB = 1,4-bis(pyrid-4yl)benzene)), and explore their applications for selective oxidation of sulfides using H 2 O 2 as an oxidant. All three compounds were catalytically effective for the oxidation of methyl phenyl sulfide to methyl phenyl sulfoxide, with 1 being best-performing with complete conversion and a selectivity of 96.7%. In the selective oxidation of a series of aromatic and aliphatic sulfides to corresponding sulfoxides, 1 also showed satisfactory performance; in particular, the chemical warfare agent stimulant 2-chloroethyl ethyl sulfide can be completely and selectively oxidized to the nontoxic 2-chloroethyl ethyl sulfoxide within 20 min at room temperature. Catalyst 1 can be recycled and reused at least six times with uncompromised performance. The perfect performance of 1 is attributed to the synergistic effect of coordinatively unsaturated V and Zn sites in bimetallic oxide, as revealed by comparative structural and catalytic studies.

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Low‐Valent Metals in Metal‐Organic Frameworks Via Post‐Synthetic Modification

Obeso,

Huxley,

de los Reyes

et al. 2023

Angewandte Chemie

0

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Metal‐organic frameworks (MOFs) provide uniquely tunable, periodic platforms for site‐isolation of reactive low‐valent metal complexes of relevance in modern catalysis, adsorptive applications, and for fundamental structural studies. Strategies for integrating such species in MOFs include, post‐synthetic metalation, encapsulation and direct synthesis using low‐valent organometallic complexes as building blocks. These approaches have each proven effective in enhancing catalytic activity, modulating product distributions (i.e., by improving catalytic selectivity), and by providing valuable mechanistic insights. In this minireview, we explore these different strategies, as applied to isolate low‐valent species within MOFs, with a particular focus on examples that leverage the unique crystallinity, permanent porosity and chemical mutability of MOFs, to achieve deep structural insights that lead to new paradigms in the field of hybrid catalysis.

show abstract

Low‐Valent Metals in Metal‐Organic Frameworks Via Post‐Synthetic Modification

Obeso,

Huxley,

de los Reyes

et al. 2023

View full text Add to dashboard Cite

Metal‐organic frameworks (MOFs) provide uniquely tunable, periodic platforms for site‐isolation of reactive low‐valent metal complexes of relevance in modern catalysis, adsorptive applications, and for fundamental structural studies. Strategies for integrating such species in MOFs include, post‐synthetic metalation, encapsulation and direct synthesis using low‐valent organometallic complexes as building blocks. These approaches have each proven effective in enhancing catalytic activity, modulating product distributions (i.e., by improving catalytic selectivity), and by providing valuable mechanistic insights. In this minireview, we explore these different strategies, as applied to isolate low‐valent species within MOFs, with a particular focus on examples that leverage the unique crystallinity, permanent porosity and chemical mutability of MOFs, to achieve deep structural insights that lead to new paradigms in the field of hybrid catalysis.

show abstract

Pyrazine-bridged molybdenum(0) carbonyl and molybdenum(VI) oxide network solids as catalysts for epoxidation and sulfoxidation

Cited by 3 publications

References 70 publications

Modulating the Catalytic Properties of Polyoxovanadates with Transition-Metal-Complex Units for Selective Oxidation of Sulfides

Modulating the Catalytic Properties of Polyoxovanadates with Transition-Metal-Complex Units for Selective Oxidation of Sulfides

Low‐Valent Metals in Metal‐Organic Frameworks Via Post‐Synthetic Modification

Low‐Valent Metals in Metal‐Organic Frameworks Via Post‐Synthetic Modification

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