The Catalytic Reduction of Azides and Hydrazines Using High-Valent Organouranium Complexes

Peters, René; Warner, Benjamin P.; Burns, Carol J.

doi:10.1021/ja9844581

Cited by 68 publications

(52 citation statements)

References 7 publications

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“…21 The presence of aniline as a product suggested the formation of U(IV) bis-anilide [Cp * 2 U(NHPh) 2 ] during the reaction, however this species could not be detected.…”

Section: Oxidative Addition With Uranium As the Only Electron Donormentioning

confidence: 99%

Uranium-mediated oxidative addition and reductive elimination

Liddle

2015

Dalton Trans.

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Oxidative addition, and its reverse reaction reductive elimination, constitute two key reactions that underpin organometallic chemistry and catalysis. Although these reactions have been known for decades in main group and transition metal systems, they are exceptionally rare or unknown for the f-block. However, in recent years much progress has been made. In this Perspective article, advances in uranium-mediated oxidative addition/reductive elimination, since the point that this research area was initiated in the early-1980s, are summarised. We principally divide the Perspective into two parts of oxidative addition and reductive elimination, along with a separate section concerning reactions where there is no change of uranium oxidation state in reactant and product but the reaction has the formal appearance of a 'concerted' reductive elimination/oxidative addition from the perspective of the net result. This body of work highlights that whilst uranium is capable of performing reactions that to some extent conform to traditional reactivity types, novel reactivity that has no counterpart anywhere else can be performed, thus adding to the rich palate of redox chemistry that uranium can mediate.

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“…21 The presence of aniline as a product suggested the formation of U(IV) bis-anilide [Cp * 2 U(NHPh) 2 ] during the reaction, however this species could not be detected.…”

Section: Oxidative Addition With Uranium As the Only Electron Donormentioning

confidence: 99%

Uranium-mediated oxidative addition and reductive elimination

Liddle

2015

Dalton Trans.

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“…There are a number of examples where transition metal and f -block metals cleave azobenzene, 9,10 but these reductions use metal complexes where the metal is in a low formal oxidation state. 11 Thus, the electrons come from the reduced metal.…”

Section: Introductionmentioning

confidence: 99%

The Mechanism of N–N Double Bond Cleavage by an Iron(II) Hydride Complex

et al. 2016

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The use of hydride species for substrate reductions avoids strong reductants, and may enable nitrogenase to reduce multiple bonds without unreasonably low redox potentials. In this work, we explore the N=N bond cleaving ability of a high-spin iron(II) hydride dimer with concomitant release of H2. Specifically, this diiron(II) reacts with azobenzene (PhN=NPh) to perform the four-electron reduction to two imido groups, where two electrons come from H2 reductive elimination and the other two come from iron oxidation. The rate law of the H2 releasing reaction indicates that diazene binding occurs prior to H2 elimination, and the negative entropy of activation and inverse kinetic isotope effect indicate that H-H bond formation is the rate-limiting step. Thus, substrate binding causes reductive elimination of H2 that formally reduces the metals, and the metals use the additional two electrons to cleave the N-N multiple bond.

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“…7, 8 Additionally, actinides have access to a wide variety of oxidation states and possess f orbitals capable of participating in bonding, allowing them to offer reactivity modes different from those of their better studied transition-metal and lanthanide counterparts. Recognition of these unique attributes has led to the discovery of actinide coordination compounds that facilitate small molecule activation, 9,10 atom-transfer reactions, 11,12 and hydrocarbon functionalization, 13,14 providing ample motivation for the development of both novel actinide systems and catalytic methodologies. 15,16 Due in large part to the kinetic and thermodynamic stability afforded via the macrocyclic effect, 17 crown ethers, 18 calixarenes, 19 and more recently "Pacman" polypyrroles 20 have been widely utilized for the study of f-element coordination chemistry and separation science.…”

Section: ■ Introductionmentioning

confidence: 99%

Synthesis and Characterization of Thorium(IV) and Uranium(IV) Corrole Complexes

et al. 2013

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The first examples of actinide complexes incorporating corrole ligands are presented. Thorium(IV) and uranium(IV) macrocycles of Mes2(p-OMePh)corrole were synthesized via salt metathesis with the corresponding lithium corrole in remarkably high yields (93% and 83%, respectively). Characterization by single-crystal X-ray diffraction revealed both complexes to be dimeric, having two metal centers bridged via bis(μ-chlorido) linkages. In each case, the corrole ring showed a large distortion from planarity, with the Th(IV) and U(IV) ions residing unusually far (1.403 and 1.330 Å, respectively) from the N4 plane of the ligand. (1)H NMR spectroscopy of both the Th and U dimers revealed dynamic solution behavior. In the case of the diamagnetic thorium corrole, variable-temperature, DOSY (diffusion-ordered) and EXSY (exhange) (1)H NMR spectroscopy was employed and supported that this behavior was due to an intrinsic pseudorotational mode of the corrole ring about the M-M axis. Additionally, the electronic structure of the actinide corroles was assessed using UV-vis spectroscopy, cyclic voltammetry, and variable-temperature magnetic susceptibility. This novel class of macrocyclic complexes provides a rich platform in an underdeveloped area for the study of nonaqueous actinide bonding and reactivity.

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The Catalytic Reduction of Azides and Hydrazines Using High-Valent Organouranium Complexes

Cited by 68 publications

References 7 publications

Uranium-mediated oxidative addition and reductive elimination

Uranium-mediated oxidative addition and reductive elimination

The Mechanism of N–N Double Bond Cleavage by an Iron(II) Hydride Complex

Synthesis and Characterization of Thorium(IV) and Uranium(IV) Corrole Complexes

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