Nitric oxide activation facilitated by cooperative multimetallic electron transfer within an iron-functionalized polyoxovanadate–alkoxide cluster

Li, F; Meyer, Rachel L.; Carpenter, Stephanie H.; VanGelder, Lauren E.; Nichols, Asa W.; Machan, Charles W.; Neidig, Michael L.; Matson, Ellen M.

doi:10.1039/c8sc00987b

Cited by 21 publications

(13 citation statements)

References 68 publications

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“…In spite of being around for many decades, electrosynthesis has recently aroused attention as it is believed to have profound impacts on organic synthesis [10–13] . For instance, anodic reactions including alcohol oxidation, [14] C−H functionalization, [15–22] alkene functionalization, [23, 24] cyclization, [25, 26] and C−O, [27] C−N, [28, 29] and C−P [30–32] couplings, and cathodic reactions including arene or alkene hydrogenation, [33, 34] and arylboronic acid hydroxylation [35] have demonstrated good selectivity and yields. Ni‐catalyzed cathodic reductive C−C homocouplings were first reported by Jennings and co‐workers in 1976.…”

Section: Introductionmentioning

confidence: 99%

Nickel‐Catalyzed Electrochemical C(sp³)−C(sp²) Cross‐Coupling Reactions of Benzyl Trifluoroborate and Organic Halides**

Luo

et al. 2021

Angew Chem Int Ed

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Reported here is the redox neutral electrochemical C(sp2)−C(sp3) cross‐coupling reaction of bench‐stable aryl halides or β‐bromostyrene (electrophiles) and benzylic trifluoroborates (nucleophiles) using nonprecious, bench‐stable NiCl2⋅glyme/polypyridine catalysts in an undivided cell configuration under ambient conditions. The broad reaction scope and good yields of the Ni‐catalyzed electrochemical coupling reactions were confirmed by 50 examples of aryl/β‐styrenyl chloride/bromide and benzylic trifluoroborates. Potential applications were demonstrated by electrosynthesis and late‐stage functionalization of pharmaceuticals and natural amino acid modification, and three reactions were run on gram‐scale in a flow‐cell electrolyzer. The electrochemical C−C cross‐coupling reactions proceed through an unconventional radical transmetalation mechanism. This method is highly productive and expected to find wide‐spread applications in organic synthesis.

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Section: Introductionmentioning

confidence: 99%

Nickel‐Catalyzed Electrochemical C(sp³)−C(sp²) Cross‐Coupling Reactions of Benzyl Trifluoroborate and Organic Halides**

Luo

et al. 2021

Angew Chem Int Ed

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“…27–28 Furthermore, there is considerable interest in the reduction/protonation of metal nitrosyl species (M(NO‧)) to produce viable HNO-releasing agents, as well as to examine the feasibility of HNO production from metal centers and NO ‧ in vivo. 24–25, 29–38…”

Section: Introductionmentioning

confidence: 99%

A Mononuclear, Nonheme Fe^II–Piloty’s Acid (PhSO₂NHOH) Adduct: An Intermediate in the Production of {FeNO}^7/8 Complexes from Piloty’s Acid

et al. 2019

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Reaction of the mononuclear nonheme complex [FeII(CH3CN)(N3PyS)]BF4 (1) with an HNO donor, Piloty’s acid (PhSO2NHOH, P.A.), at low temperature affords a high-spin (S = 2) FeII-P.A. intermediate (2), characterized by 57Fe Mössbauer and Fe K- edge X-ray absorption (XAS) spectroscopies, with interpretation of both supported by DFT calculations. The combined methods indicate that P.A. anion binds as the N-deprotonated tautomer (PhSO2NOH−) to [FeII(N3PyS)]+, leading to 2. Complex 2 is the first spectroscopically characterized example, to our knowledge, of P.A. anion bound to a redox-active metal center. Warming of 2 above −60 °C yields the stable {FeNO}7 complex [Fe(NO)(N3PyS)]BF4 (4), as evidenced by 1H NMR, ATR-IR, and Mössbauer spectroscopies. Isotope labeling experiments with 15N-labeled P.A. confirm that the nitrosyl ligand in 4 derives from P.A. In contrast, addition of a second equivalent of a strong base leads to S-N cleavage and production of an {FeNO}8 species, the deprotonated analog of an Fe-HNO complex. This work has implications for the targeted delivery of HNO/ NO−/NO‧ to nonheme Fe centers in biological and synthetic applications, and suggests a new role for nonheme FeII complexes in the assisted degradation of HNO donor molecules.

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“…Also, the rod‐like Na 6 [V 10 O 28 ]·16H 2 O compounds exhibit decent sodium‐ion storage performance . Besides, polyoxovanadate directs the growth of two‐dimensional hydroxide nanosheets, leading to desired porosity and an charge reservoir for capacitor application, and polyoxovanadate containing iron is synthesized to form polyoxovanadate‐alkoxide cluster and ensure large amount of electron transfer …”

Section: Polyoxovanadatementioning

confidence: 99%

Polyoxometalates: Tailoring metal oxides in molecular dimension toward energy applications

Zhang

Chen

2020

Int J Energy Res

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Summary Polyoxometalates could be viewed as the molecular counterpart of the metal oxides, which are essential ingredients for various energy conversion and storage applications. In this manuscript, we review the progress of engineering functional polyoxometalates toward energy applications, focusing on, but not limited to, polyoxotitanate, polyoxotungstate, and polyoxomolybdate. These polyoxometalates are considered to be promising candidates for dye‐sensitized solar cell, perovskite solar cell, lithium‐ion battery, lithium‐sulfur battery, supercapacitor, and water‐splitting system. We believe advanced energy devices with better performance could be derived from further engineering the polyoxometalates owing to their molecular design flexibility.

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Nitric oxide activation facilitated by cooperative multimetallic electron transfer within an iron-functionalized polyoxovanadate–alkoxide cluster

Abstract: Cooperative multimetallic electron transfer to accommodate substrate binding.

Cited by 21 publications

References 68 publications

Nickel‐Catalyzed Electrochemical C(sp³)−C(sp²) Cross‐Coupling Reactions of Benzyl Trifluoroborate and Organic Halides**

Nickel‐Catalyzed Electrochemical C(sp³)−C(sp²) Cross‐Coupling Reactions of Benzyl Trifluoroborate and Organic Halides**

A Mononuclear, Nonheme Fe^II–Piloty’s Acid (PhSO₂NHOH) Adduct: An Intermediate in the Production of {FeNO}^7/8 Complexes from Piloty’s Acid

Polyoxometalates: Tailoring metal oxides in molecular dimension toward energy applications

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Nitric oxide activation facilitated by cooperative multimetallic electron transfer within an iron-functionalized polyoxovanadate–alkoxide cluster

Abstract: Cooperative multimetallic electron transfer to accommodate substrate binding.

Cited by 21 publications

References 68 publications

Nickel‐Catalyzed Electrochemical C(sp3)−C(sp2) Cross‐Coupling Reactions of Benzyl Trifluoroborate and Organic Halides**

Nickel‐Catalyzed Electrochemical C(sp3)−C(sp2) Cross‐Coupling Reactions of Benzyl Trifluoroborate and Organic Halides**

A Mononuclear, Nonheme FeII–Piloty’s Acid (PhSO2NHOH) Adduct: An Intermediate in the Production of {FeNO}7/8 Complexes from Piloty’s Acid

Polyoxometalates: Tailoring metal oxides in molecular dimension toward energy applications

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Resources

About

Nickel‐Catalyzed Electrochemical C(sp³)−C(sp²) Cross‐Coupling Reactions of Benzyl Trifluoroborate and Organic Halides**

Nickel‐Catalyzed Electrochemical C(sp³)−C(sp²) Cross‐Coupling Reactions of Benzyl Trifluoroborate and Organic Halides**

A Mononuclear, Nonheme Fe^II–Piloty’s Acid (PhSO₂NHOH) Adduct: An Intermediate in the Production of {FeNO}^7/8 Complexes from Piloty’s Acid