The photochemical reaction between uranyl nitrate and azulene

Cardoso, A. C.; Formosinho, Sebastião J.; Gil, Ana M.; Miguel, Maria; Barata, Belamino; Moura, José J. G.

doi:10.1016/1010-6030(92)85237-o

Cited by 11 publications

(4 citation statements)

References 18 publications

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“…Even though the oxidation of organic substrates by *UO 2 2+ is fairly common, ,,,,− such reactions typically take place by hydrogen atom abstraction or initial addition to multiple bonds. To our knowledge, an outer-sphere electron transfer between *UO 2 2+ and a hydrocarbon has not been reported previously.…”

Section: Discussionmentioning

confidence: 99%

Uranyl-Sensitized Photochemical Oxidation of Naphthalene by Molecular Oxygen. Role of Electron Transfer

Mao

Bakač

1997

J. Phys. Chem. A

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Naphthalene quenches the excited state *UO2 2+ in two parallel pathways: oxidation to naphthalene radical cation, C10H8 •+ (Φ = 0.3), and exciplex formation. The overall rate constant in aqueous acetonitrile containing 0.1 M H3PO4 has a value k q = 2.20 × 109 M-1 s-1. In the presence of O2, a portion of C10H8 •+ is converted to 2-formylcinnamaldehyde and several other products, the rest reacting with UO2 + by back electron transfer.

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Section: Discussionmentioning

confidence: 99%

Uranyl-Sensitized Photochemical Oxidation of Naphthalene by Molecular Oxygen. Role of Electron Transfer

Mao

Bakač

1997

J. Phys. Chem. A

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“…+2.6 V, comparable to F 2 ) excited state of uranyl. , Subsequent ligand-to-metal charge transfer (LMCT) that arises from U(5 f ) ← O(2 p ) transitions generates the [U V O 2 ] + 5 f 1 intermediate which contains an extremely reactive oxyl radical, O • (Scheme b). This intermediate may generally be quenched by H atom abstraction (HAA) if the quencher is aliphatic (to give a functionalized [OU V –OH] 2+ motif) − or by electron transfer if the quencher is unsaturated. − The highly oxidizing nature of photoactivated [U VI O 2 ] 2+ has previously been exploited in the degradation of volatile organic compounds, VOCs, such as methanol, and many other applications, including in metal ion sensing and biochemistry, have been developed since the last reviews appeared in 2010 and 2013. ,,, …”

Section: Introductionmentioning

confidence: 99%

Thermal and Photochemical Reduction and Functionalization Chemistry of the Uranyl Dication, [U^VIO₂]²⁺

et al. 2019

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The uranyl ion, [UVIO2]2+, possesses rigorously trans, strongly covalent, and chemically robust U-oxo groups. However, through the use of anaerobic reaction techniques, both one- and two-electron reductive functionalization of the uranyl oxo groups has been discovered and developed. Prior to 2010, this unusual reactivity centered around the reductive silylation of the uranyl ion which entailed conversion of the oxo ligands into siloxy ligands and reductive metalation of the uranyl oxo with Group 1 and f-block metals. This review surveys the large number of new examples of reductive functionalization of the uranyl ion that have been reported since 2010, including reductive borylation and alumination, metalation with d- or f-block metals, and new examples of reductive silylation. Other examples of oxo-group functionalization of [UVIO2]2+ that do not involve reduction, mainly with Group 1 cations, are also covered, along with new advances in the photochemistry of the uranyl(VI) ion that involve the transient formation of formally uranyl(V) [UVO2]+ ion.

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“…The electronic structure and photochemistry − of uranyl ion have recently been reviewed. Photooxidation of substrates by *UO 2 2+ is thought to occur by both atom − and electron-transfer ,,− processes. With phenols, reaction has been shown to occur by a dynamic process 25 involving intermediate phenoxyl radical−uranium(V) radical pairs. , Although many of the early studies on photooxidation of phenols by uranyl ion concentrated on the kinetics of these processes, we have recently reported results of a combined study of the kinetics and product characterization on the uranyl-ion-sensitized photolysis of 2,6-dimethylphenol and monophenylphenols in aqueous solution .…”

Section: Introductionmentioning

confidence: 99%

Electron-Transfer Oxidation of Chlorophenols by Uranyl Ion Excited State in Aqueous Solution. Steady-State and Nanosecond Flash Photolysis Studies

2000

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The oxidation of chlorophenols by photoexcited uranyl ion was studied in aqueous solution at concentrations where the ground-state interactions were negligible. Nanosecond flash photolysis showed that a clean electrontransfer process from the chlorophenols to the excited uranyl ion is involved. This is suggested to lead to the formation of a U(V)/chlorophenoxyl radical pair complex. The efficiency of this charge-transfer process is unity for the three chlorophenols. However, low product yields suggest that in the absence of oxygen, back electron transfer, both within the radical pair and from separated uranium(V) to phenoxyl radicals, appears to be the major reaction pathway. In the presence of oxygen the quantum yields of disappearance of chlorophenol and of photoproduct formation increased. This leads to the conclusion that oxygen favors reaction with uranium(V) and/or the uranium(V)-phenoxyl radical pair, leading to the formation of the superoxide anion and its conjugate acid, HO 2 • , which then regenerate UO 2 2+. Based on this, a catalytic cycle for chlorophenol photooxidation involving uranyl ion and molecular oxygen is proposed.

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The photochemical reaction between uranyl nitrate and azulene

Cited by 11 publications

References 18 publications

Uranyl-Sensitized Photochemical Oxidation of Naphthalene by Molecular Oxygen. Role of Electron Transfer

Uranyl-Sensitized Photochemical Oxidation of Naphthalene by Molecular Oxygen. Role of Electron Transfer

Thermal and Photochemical Reduction and Functionalization Chemistry of the Uranyl Dication, [U^VIO₂]²⁺

Electron-Transfer Oxidation of Chlorophenols by Uranyl Ion Excited State in Aqueous Solution. Steady-State and Nanosecond Flash Photolysis Studies

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The photochemical reaction between uranyl nitrate and azulene

Cited by 11 publications

References 18 publications

Uranyl-Sensitized Photochemical Oxidation of Naphthalene by Molecular Oxygen. Role of Electron Transfer

Uranyl-Sensitized Photochemical Oxidation of Naphthalene by Molecular Oxygen. Role of Electron Transfer

Thermal and Photochemical Reduction and Functionalization Chemistry of the Uranyl Dication, [UVIO2]2+

Electron-Transfer Oxidation of Chlorophenols by Uranyl Ion Excited State in Aqueous Solution. Steady-State and Nanosecond Flash Photolysis Studies

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Thermal and Photochemical Reduction and Functionalization Chemistry of the Uranyl Dication, [U^VIO₂]²⁺