In situ beam reduction of Pu(IV) and Bk(IV) as a route to trivalent transuranic coordination complexes with hydroxypyridinone chelators.

The solution-state interactions of plutonium and berkelium with the octadentate chelator 3,4,3-LI(1,2-HOPO) (343-HOPO) were investigated and characterized by X-ray absorption spectroscopy, which revealed in situ reductive decomposition of the tetravalent species of both actinide metals to yield Pu(III) and Bk(III) coordination complexes. X-ray absorption near-edge structure (XANES) measurements were the first indication of in situ synchrotron redox chemistry as the Pu threshold and white-line position energies for Pu-343-HOPO were in good agreement with known diagnostic Pu(III) species, whereas Bk-343-HOPO results were found to mirror the XANES behavior of Bk(III)-DTPA. Extended X-ray absorption fine structure results revealed An-O bond distances of 2.

Increasing reactivity by incorporating π-acceptor ligands into coordinatively unsaturated thiolate-ligated iron(II) complexes.

Reported herein is the structural, spectroscopic, redox, and reactivity properties of a series of iron complexes containing both a π-donating thiolate, and π-accepting -heterocycles in the coordination sphere, in which we systematically vary the substituents on the -heterocycle, the size of the -heterocycle, and the linker between the imine nitrogen and tertiary amine nitrogen. In contrast to our primary amine/thiolate-ligated Fe(II) complex, [Fe(SN(tren))] (), the Fe(II) complexes reported herein are intensely colored, allowing us to visually monitor reactivity. Ferrous complexes with R = H substituents in the 6-position of the pyridines, [Fe(SN(6-H-DPPN)] () and [Fe(SN(6-H-DPEN))(MeOH)] () are shown to readily bind neutral ligands, and all of the Fe(II) complexes are shown to bind anionic ligands regardless of steric congestion.

Combining the Best of Two Chelating Titans: A Hydroxypyridinone-Decorated Macrocyclic Ligand for Efficient and Concomitant Complexation and Sensitized Luminescence of f-Elements.

An ideal chelator for f-elements features rapid kinetics of complexation, high thermodynamic stability, and slow kinetics of dissociation. Here we present the facile synthesis of a macrocyclic ligand bearing four 1-hydroxy-2-pyridinone units linked to a cyclen scaffold that rapidly forms thermodynamically stable complexes with lanthanides (Sm , Eu , Tb , Dy ) and a representative late actinide (Cm ) in aqueous media and concurrently sensitizes them. Extended X-ray absorption fine structure (EXAFS) spectroscopy revealed an increase in the Ln/An-O bond lengths following the trend Cm>Eu>Tb and EXAFS data were compatible with time-resolved luminescence studies, which indicated one to two water molecules in the inner metal coordination sphere of Eu(III) and two water molecules for the Cm(III) complex.

Controlling the Reduction of Chelated Uranyl to Stable Tetravalent Uranium Coordination Complexes in Aqueous Solution.

The solution-state interactions between octadentate hydroxypyridinone (HOPO) and catecholamide (CAM) chelating ligands and uranium were investigated and characterized by UV-visible spectrophotometry and X-ray absorption spectroscopy (XAS), as well as electrochemically via spectroelectrochemistry (SEC) and cyclic voltammetry (CV) measurements. Depending on the selected chelator, we demonstrate the controlled ability to bind and stabilize U, generating with 3,4,3-LI(1,2-HOPO), a tetravalent uranium complex that is practically inert toward oxidation or hydrolysis in acidic, aqueous solution. At physiological pH values, we are also able to bind and stabilize U to a lesser extent, as evidenced by the mix of U and U complexes observed via XAS.

Evaluating Ac and Lu Radioimmunoconjugates against Antibody-Drug Conjugates for Small-Cell Lung Cancer.

Interest in the use of Ac for targeted alpha therapies has increased dramatically over the past few years, resulting in a multitude of new isotope production and translational research efforts. However, Ac radioimmunoconjugate (RIC) research is still in its infancy, with most prior experience in hematologic malignancies and only one reported preclinical solid tumor study using Ac RICs. In an effort to compare Ac RICs to other current antibody conjugates, a variety of RICs are tested against intractable small-cell lung cancer (SCLC).

Structural properties of ultra-small thorium and uranium dioxide nanoparticles embedded in a covalent organic framework.

We report the structural properties of ultra-small ThO and UO nanoparticles (NPs), which were synthesized without strong binding surface ligands by employing a covalent organic framework (COF-5) as an inert template. The resultant NPs were used to observe how structural properties are affected by decreasing grain size within bulk actinide oxides, which has implications for understanding the behavior of nuclear fuel materials. Through a comprehensive characterization strategy, we gain insight regarding how structure at the NP surface differs from the interior.

Spontaneous Chelation-Driven Reduction of the Neptunyl Cation in Aqueous Solution.

Octadentate hydroxypyridinone (HOPO) and catecholamide (CAM) siderophore analogues are known to be efficacious chelators of the actinide cations, and these ligands are also capable of facilitating both activation and reduction of actinyl species. Utilizing X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies, as well as cyclic voltammetry measurements, herein, we elucidate chelation-based mechanisms for driving reactivity and initiating redox processes in a family of neptunyl-HOPO and CAM complexes. Based on the selected chelator, the ability to control the oxidation state of neptunium and the speed of reduction and concurrent oxo group activation was demonstrated.

How Metal Ion Lewis Acidity and Steric Properties Influence the Barrier to Dioxygen Binding, Peroxo O-O Bond Cleavage, and Reactivity.

Herein we quantitatively investigate how metal ion Lewis acidity and steric properties influence the kinetics and thermodynamics of dioxygen binding versus release from structurally analogous Mn-O complexes, as well as the barrier to Mn peroxo O-O bond cleavage, and the reactivity of Mn oxo intermediates. Previously we demonstrated that the steric and electronic properties of Mn-OOR complexes containing N-heterocyclic (N) ligand scaffolds can have a dramatic influence on alkylperoxo O-O bond lengths and the barrier to alkylperoxo O-O bond cleavage. Herein, we examine the dioxygen reactivity of a new Mn complex containing a more electron-rich, less sterically demanding N ligand scaffold, and compare it with previously reported Mn complexes.

Evaluating the potential of chelation therapy to prevent and treat gadolinium deposition from MRI contrast agents.

Several MRI contrast agent clinical formulations are now known to leave deposits of the heavy metal gadolinium in the brain, bones, and other organs of patients. This persistent biological accumulation of gadolinium has been recently recognized as a deleterious outcome in patients administered Gd-based contrast agents (GBCAs) for MRI, prompting the European Medicines Agency to recommend discontinuing the use of over half of the GBCAs currently approved for clinical applications. To address this problem, we find that the orally-available metal decorporation agent 3,4,3-LI(1,2-HOPO) demonstrates superior efficacy at chelating and removing Gd from the body compared to diethylenetriaminepentaacetic acid, a ligand commonly used in the United States in the GBCA Gadopentetate (Magnevist).

How Do Ring Size and π-Donating Thiolate Ligands Affect Redox-Active, α-Imino-N-heterocycle Ligand Activation?

Considerable effort has been devoted to the development of first-row transition-metal catalysts containing redox-active imino-pyridine ligands that are capable of storing multiple reducing equivalents. This property allows abundant and inexpensive first-row transition metals, which favor sequential one-electron redox processes, to function as competent catalysts in the concerted two-electron reduction of substrates. Herein we report the syntheses and characterization of a series of iron complexes that contain both π-donating thiolate and π-accepting (α-imino)-N-heterocycle redox-active ligands, with progressively larger N-heterocycle rings (imidazole, pyridine, and quinoline).

Iron L-Edge X-ray Absorption and X-ray Magnetic Circular Dichroism Studies of Molecular Iron Complexes with Relevance to the FeMoco and FeVco Active Sites of Nitrogenase.

Herein, a systematic study of a series of molecular iron model complexes has been carried out using Fe L-edge X-ray absorption (XAS) and X-ray magnetic circular dichroism (XMCD) spectroscopies. This series spans iron complexes of increasing complexity, starting from ferric and ferrous tetrachlorides ([FeCl]), to ferric and ferrous tetrathiolates ([Fe(SR)]), to diferric and mixed-valent iron-sulfur complexes [FeSR]. This test set of compounds is used to evaluate the sensitivity of both Fe L-edge XAS and XMCD spectroscopy to oxidation state and ligation changes.

Electronic Structure of a Formal Iron(0) Porphyrin Complex Relevant to CO Reduction.

Iron porphyrins can act as potent electrocatalysts for CO functionalization. The catalytically active species has been proposed to be a formal Fe(0) porphyrin complex, [Fe(TPP)] (TPP = tetraphenylporphyrin), generated by two-electron reduction of [Fe(TPP)]. Our combined spectroscopic and computational investigations reveal that the reduction is ligand-centered and that [Fe(TPP)] is best formulated as an intermediate-spin Fe(II) center that is antiferromagnetically coupled to a porphyrin diradical anion, yielding an overall singlet ground state.

Two Exceptional Homoleptic Iron(IV) Tetraalkyl Complexes.

The formation of the high-valent iron complex [Fe(cyclohexyl) ] from Fe under reducing conditions is best explained by disproportionation of a transient organoiron intermediate which is driven by dispersive forces between the cyclohexyl ligands and the formation of short and strong Fe-C bonds. The (meta)stability of this diamagnetic complex (S=0) is striking if one considers that it has empty d-orbitals at its disposal and contains, at the same time, no less than twenty H-atoms available for either α- or β-hydride elimination.

Comparative electronic structures of nitrogenase FeMoco and FeVco.

An investigation of the active site cofactors of the molybdenum and vanadium nitrogenases (FeMoco and FeVco) was performed using high-resolution X-ray spectroscopy. Synthetic heterometallic iron-sulfur cluster models and density functional theory calculations complement the study of the MoFe and VFe holoproteins using both non-resonant and resonant X-ray emission spectroscopy. Spectroscopic data show the presence of direct iron-heterometal bonds, which are found to be weaker in FeVco.

Metal-Assisted Oxo Atom Addition to an Fe(III) Thiolate.

Cysteinate oxygenation is intimately tied to the function of both cysteine dioxygenases (CDOs) and nitrile hydratases (NHases), and yet the mechanisms by which sulfurs are oxidized by these enzymes are unknown, in part because intermediates have yet to be observed. Herein, we report a five-coordinate bis-thiolate ligated Fe(III) complex, [Fe(SN(Pr,Pr))] (2), that reacts with oxo atom donors (PhIO, IBX-ester, and HO) to afford a rare example of a singly oxygenated sulfenate, [Fe(η-SO)(S)N(Pr,Pr)] (5), resembling both a proposed intermediate in the CDO catalytic cycle and the essential NHase Fe-S(O) proposed to be intimately involved in nitrile hydrolysis. Comparison of the reactivity of 2 with that of a more electron-rich, crystallographically characterized derivative, [FeSNN(Pr,Pr)] (8), shows that oxo atom donor reactivity correlates with the metal ion's ability to bind exogenous ligands.

Experimental and theoretical correlations between vanadium K-edge X-ray absorption and Kβ emission spectra.

A series of vanadium compounds was studied by K-edge X-ray absorption (XAS) and K[Formula: see text] X-ray emission spectroscopies (XES). Qualitative trends within the datasets, as well as comparisons between the XAS and XES data, illustrate the information content of both methods. The complementary nature of the chemical insight highlights the success of this dual-technique approach in characterizing both the structural and electronic properties of vanadium sites.

Complete Series of {FeNO}(8), {FeNO}(7), and {FeNO}(6) Complexes Stabilized by a Tetracarbene Macrocycle.

Use of a macrocyclic tetracarbene ligand, which is topologically reminiscent of tetrapyrrole macrocycles though electronically distinct, has allowed for the isolation, X-ray crystallographic characterization and comprehensive spectroscopic investigation of a complete set of {FeNO}(x) complexes (x = 6, 7, 8). Electrochemical reduction, or chemical reduction with CoCp2, of the {FeNO}(7) complex 1 leads to the organometallic {FeNO}(8) species 2. Its crystallographic structure determination is the first for a nonheme iron nitroxyl {FeNO}(8) and has allowed to identify structural trends among the series of {FeNO}(x) complexes.

The Fe-V Cofactor of Vanadium Nitrogenase Contains an Interstitial Carbon Atom.

The first direct evidence is provided for the presence of an interstitial carbide in the Fe-V cofactor of Azotobacter vinelandii vanadium nitrogenase. As for our identification of the central carbide in the Fe-Mo cofactor, we employed Fe Kβ valence-to-core X-ray emission spectroscopy and density functional theory calculations, and herein report the highly similar spectra of both variants of the cofactor-containing protein. The identification of an analogous carbide, and thus an atomically homologous active site in vanadium nitrogenase, highlights the importance and influence of both the interstitial carbide and the identity of the heteroatom on the electronic structure and catalytic activity of the enzyme.

X-ray Absorption and Emission Study of Dioxygen Activation by a Small-Molecule Manganese Complex.

Manganese K-edge X-ray absorption (XAS) and Kβ emission (XES) spectroscopies were used to investigate the factors contributing to O-O bond activation in a small-molecule system. The recent structural characterization of a metastable peroxo-bridged dimeric Mn(III)2 complex derived from dioxygen has provided the first opportunity to obtain X-ray spectroscopic data on this type of species. Ground state and time-dependent density functional theory calculations have provided further insight into the nature of the transitions in XAS pre-edge and valence-to-core (VtC) XES spectral regions.