Visible light generation of high-valent metal-oxo intermediates and mechanistic insights into catalytic oxidations

First‐Row Transition‐Metal Complexes with Tetra‐Amido Macrocyclic Ligands for Water and C(sp3)−H Bond Oxidation: Performance Benchmarking Using Free Energy Relationships

“…In electrochemical and photochemical oxidation methods, H 2 O is used as an oxygen source for the in situ generation of metal-oxo species to catalytically oxidize C(sp 3 )À H bonds. [78,79]…”

“…Chemical oxidation methods employ oxygen‐containing oxidants such as iodosobenzene (PhIO) or meta ‐chloroperoxybenzoic acid ( m CPBA). In electrochemical and photochemical oxidation methods, H 2 O is used as an oxygen source for the in situ generation of metal‐oxo species to catalytically oxidize C(sp 3 )−H bonds [78,79] …”

Rhodamine B oxidation promoted by P450-bioinspired Jacobsen catalysts/cellulose systems

“…9 Among numerous proposals to mimic monooxygenase active sites, metal-Schiff base complexes stand out, especially Jacobsen chiral catalysts. 12,[33][34][35][36][37][38] These salen complexes are efficient catalysts in homogeneous and heterogeneous environment reactions such as olen ring opening and polymerization, 39,40 allyl alkylation, 41 alkene epoxidation, 12,42,43 alkane oxidation, 38 and drug oxidation 37,[44][45][46][47] and act as P450 cytochromes model systems. 10,12,25,38,45,[48][49][50][51][52] An advantage of the Jacobsen complex is its simple preparation, for example, it can be synthesized on a large scale (in the order of kilograms) at a low cost (US$41.40 per gram).…”

“…12,[33][34][35][36][37][38] These salen complexes are efficient catalysts in homogeneous and heterogeneous environment reactions such as olen ring opening and polymerization, 39,40 allyl alkylation, 41 alkene epoxidation, 12,42,43 alkane oxidation, 38 and drug oxidation 37,[44][45][46][47] and act as P450 cytochromes model systems. 10,12,25,38,45,[48][49][50][51][52] An advantage of the Jacobsen complex is its simple preparation, for example, it can be synthesized on a large scale (in the order of kilograms) at a low cost (US$41.40 per gram). 53 Furthermore, biomimetic chemistry has increasingly investigated the role of the protein matrix surrounding the CYP heme group, 32 which controls active oxidant reactivity and prevents a Grupo de Pesquisa em Bioinorgânica e Catálise (GPBioCat), Departamento de Química Geral e Inorgânica, IQ-UFBA, R. Barão de Jeremoabo 147, Campus de Ondina, 40170-115 Salvador, BA, Brazil.…”

Photochemical generation and reactivity of a new phthalocyanine-manganese–oxo intermediate

“…On the contrary, most chemical methods rely on the use of toxic or polluting reagents. In this regard, our previously published works 28,29 have demonstrated that the photochemical production of high-valent transition metal-oxo derivatives is a promising approach with general synthetic utility. As a result, various transition metal-oxo intermediates containing different metals on macrocyclic systems, such as porphyrin, [30][31][32][33][34] corrole 35,36 and salen ligands 37 have been successfully produced and studied in real time.…”