The iron-nitrato/iron-nitrosyl couple in the presence of hexamethylphosphoric triamide and its relevance to oxygen activation and transfer. X-ray structure of Fe(NO3)(Cl)2(HMPA)2

Wah, Henri Li Kam; Postel, M.; Tomi, F.

doi:10.1021/ic00301a015

Cited by 31 publications

(5 citation statements)

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“…Oxidation of Pd–NO species to Pd–NO 2 and Pd–NO 3 species is reported, and there is an interesting complementarity here with iron–nitrato/iron–-nitrosyl chemistry. , …”

Section: Discussionmentioning

confidence: 74%

Redox Couple Involving NO_x in Aerobic Pd-Catalyzed Oxidation of sp³-C–H Bonds: Direct Evidence for Pd–NO₃^–/NO₂^– Interactions Involved in Oxidation and Reductive Elimination

et al. 2017

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NaNO is used in oxidative Pd-catalyzed processes as a complementary co-catalyst to common oxidants, e.g., Cu salts, in C-H bond activation and Wacker oxidation processes. NaNO and NaNO (with air or O) assist the sp-C-H bond acetoxylation of substrates bearing an N-directing group. It has been proposed previously that a redox couple is operative. The role played by NO anions is examined in this investigation. Evidence for an NO anion interaction at Pd is presented. Palladacyclic complexes containing NO anions are competent catalysts for acetoxylation of 8-methylquinoline, with and without exogenous NaNO. The oxidation of 8-methylquinoline to the corresponding carboxylic acid has also been noted at Pd. O-Labeling studies indicate that oxygen derived from nitrate appears in the acetoxylation product, the transfer of which can only occur by interaction ofO at Pd with a coordinating-acetate ligand. Nitrated organic intermediates are formed under catalytic conditions, which are converted to acetoxylation products, a process that occurs with (50 °C) and without Pd (110 °C). A catalytically competent palladacyclic dimer intermediate has been identified. Head-space analysis measurements show that NO and NO gases are formed within minutes on heating catalytic mixtures to 110 °C from room temperature. Measurements by in situ infrared spectroscopy show that NO is formed in sp-C-H acetoxylation reactions at 80 °C. Studies confirm that cyclopalladated NO complexes are rapidly oxidized to the corresponding NO adducts on exposure to NO(g). The investigation shows that NO anions act as participating ligands at Pd in aerobic sp-C-H bond acetoxylation processes and are involved in redox processes.

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“…Oxidation of Pd–NO species to Pd–NO 2 and Pd–NO 3 species is reported, and there is an interesting complementarity here with iron–nitrato/iron–-nitrosyl chemistry. , …”

Section: Discussionmentioning

confidence: 74%

Redox Couple Involving NO_x in Aerobic Pd-Catalyzed Oxidation of sp³-C–H Bonds: Direct Evidence for Pd–NO₃^–/NO₂^– Interactions Involved in Oxidation and Reductive Elimination

et al. 2017

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“…The resulting nitrato compound is capable of O atom transfer to PPh 3 or cyclohexene, demonstrating the first example of O atom transfer from a nitrato ligand to an olefin. Postel and coworkers further noticed that the O-atom transfer ability of the iron nitrato complexes is dependent on the number of ligands bound to iron . When a sterically demanding DNIC, [(HMPA)(Cl)Fe(NO) 2 ] ( 66 ), was used, oxygenation resulted in several different types of iron nitrato complexes of which only 5C nitrate complexes, such as [Fe(NO 3 ) 2 Cl(HMPA) 2 ] or [Fe(NO 3 )Cl 2 (HMPA) 2 ], are capable of transferring O atoms to phosphines, while 4C nitrate complexes have no oxidizing capability.…”

Section: Dinitrosyl Iron Complexes (Dnics)mentioning

confidence: 99%

“…When a sterically demanding DNIC, [(HMPA)(Cl)Fe(NO) 2 ] ( 66 ), was used, oxygenation resulted in several different types of iron nitrato complexes of which only 5C nitrate complexes, such as [Fe(NO 3 ) 2 Cl(HMPA) 2 ] or [Fe(NO 3 )Cl 2 (HMPA) 2 ], are capable of transferring O atoms to phosphines, while 4C nitrate complexes have no oxidizing capability. The authors suggested that the enhanced electron density on the Fe(NO 3 ) 2 moiety is a key factor for the oxygenation step …”

Section: Dinitrosyl Iron Complexes (Dnics)mentioning

confidence: 99%

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

et al. 2021

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Nitric oxide (NO) is an important signaling molecule that is involved in a wide range of physiological and pathological events in biology. Metal coordination chemistry, especially with iron, is at the heart of many biological transformations involving NO. A series of heme proteins, nitric oxide synthases (NOS), soluble guanylate cyclase (sGC), and nitrophorins, are responsible for the biosynthesis, sensing, and transport of NO. Alternatively, NO can be generated from nitrite by heme- and copper-containing nitrite reductases (NIRs). The NO-bearing small molecules such as nitrosothiols and dinitrosyl iron complexes (DNICs) can serve as an alternative vehicle for NO storage and transport. Once NO is formed, the rich reaction chemistry of NO leads to a wide variety of biological activities including reduction of NO by heme or non-heme iron-containing NO reductases and protein post-translational modifications by DNICs. Much of our understanding of the reactivity of metal sites in biology with NO and the mechanisms of these transformations has come from the elucidation of the geometric and electronic structures and chemical reactivity of synthetic model systems, in synergy with biochemical and biophysical studies on the relevant proteins themselves. This review focuses on recent advancements from studies on proteins and model complexes that not only have improved our understanding of the biological roles of NO but also have provided foundations for biomedical research and for bio-inspired catalyst design in energy science.

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“…The oxidation mechanism in the presence of iron nitrate is believed to proceed by the formation of an olefin-nitrate complex followed by the insertion of an oxygen atom of the coordinated nitrate into the substrate, resulting in the oxidized product. 29 This is immediately followed by the recombination of the iron-nitrosyl intermediate with dioxygen. In addition to this, Fe 3+ ions in the presence of oxygen atmosphere may also undergo reduction to the lower valent state (Fe 2+ ), further enhancing the oxidizing capacity of the metal nitrate salt.…”

Section: Green Contextmentioning

confidence: 99%

An efficient and ecofriendly oxidation of alkenes using iron nitrate and molecular oxygen

et al. 2002

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The iron-nitrato/iron-nitrosyl couple in the presence of hexamethylphosphoric triamide and its relevance to oxygen activation and transfer. X-ray structure of Fe(NO3)(Cl)2(HMPA)2

Cited by 31 publications

References 2 publications

Redox Couple Involving NO_x in Aerobic Pd-Catalyzed Oxidation of sp³-C–H Bonds: Direct Evidence for Pd–NO₃^–/NO₂^– Interactions Involved in Oxidation and Reductive Elimination

Redox Couple Involving NO_x in Aerobic Pd-Catalyzed Oxidation of sp³-C–H Bonds: Direct Evidence for Pd–NO₃^–/NO₂^– Interactions Involved in Oxidation and Reductive Elimination

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

An efficient and ecofriendly oxidation of alkenes using iron nitrate and molecular oxygen

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The iron-nitrato/iron-nitrosyl couple in the presence of hexamethylphosphoric triamide and its relevance to oxygen activation and transfer. X-ray structure of Fe(NO3)(Cl)2(HMPA)2

Cited by 31 publications

References 2 publications

Redox Couple Involving NOx in Aerobic Pd-Catalyzed Oxidation of sp3-C–H Bonds: Direct Evidence for Pd–NO3–/NO2– Interactions Involved in Oxidation and Reductive Elimination

Redox Couple Involving NOx in Aerobic Pd-Catalyzed Oxidation of sp3-C–H Bonds: Direct Evidence for Pd–NO3–/NO2– Interactions Involved in Oxidation and Reductive Elimination

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

An efficient and ecofriendly oxidation of alkenes using iron nitrate and molecular oxygen

Contact Info

Product

Resources

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Redox Couple Involving NO_x in Aerobic Pd-Catalyzed Oxidation of sp³-C–H Bonds: Direct Evidence for Pd–NO₃^–/NO₂^– Interactions Involved in Oxidation and Reductive Elimination

Redox Couple Involving NO_x in Aerobic Pd-Catalyzed Oxidation of sp³-C–H Bonds: Direct Evidence for Pd–NO₃^–/NO₂^– Interactions Involved in Oxidation and Reductive Elimination