F-element Chemistry Research Articles

Utility of all-pyrazole heteroscorpionates in f-element chemistry.

Since their discovery in 1966, scorpionate ligands have been utilized to make coordination compounds for a variety of applications such as: studying organometallic reactions, biomimetic complexes, light-emitting materials and single-ion magnets. The recent development of a solvent-free pyrazole substitution chemistry has yielded the quantitative synthesis of asymmetrically functionalized all-pyrazole heteroscorpionate ligands. In this frontier article, we highlight the utility of all-pyrazole heteroscorpionates, specifically, nitro-trispyrazolylborates, in f-element chemistry. They offer great versatility in coordinating ability, donor strength, steric bulk and even optical charge transfer properties, all of which can be used to tune the properties of resultant complexes with metal ions. We show how they can impart structural diversity, sensitize Ln3+ luminescence and engender magnetic anisotropy and slow magnetic relaxation in the ion they coordinate. Additionally, we comment on the future of functionalized trispyrazolyl scorpionates, which includes enabling post-synthetic modifications of f-element complexes and becoming a platform to study the electronic properties of low oxidation state actinides.

A comparison between the one- and two-step spin-orbit coupling approaches based on the ab initio density matrix renormalization group.

The efficient and reliable treatment of both spin-orbit coupling (SOC) and electron correlation is essential for understanding f-element chemistry. We analyze two approaches to the problem: the one-step approach, where both effects are treated simultaneously, and the two-step state interaction approach. We report an implementation of the ab initio density matrix renormalization group with a one-step treatment of the SOC effect, which can be compared to prior two-step treatments on an equal footing. Using a dysprosium octahedral complex and bridged dimer as benchmark systems, we identify characteristics of problems where the one-step approach is beneficial for obtaining the low-energy spectrum.

Reactivity of Multimetallic Thorium Nitrides Generated by Reduction of Thorium Azides.

Thorium nitrides are likely intermediates in the reported cleavage and functionalization of dinitrogen by molecular thorium complexes and are attractive compounds for the study of multiple bond formation in f-element chemistry, but only one example of thorium nitride isolable from solution was reported. Here, we show that stable multimetallic azide/nitride thorium complexes can be generated by reduction of thorium azide precursors─a route that has failed so far to produce Th nitrides. Once isolated, the thorium azide/nitride clusters, M3Th═N═Th (M = K or Cs), are stable in solutions probably due to the presence of alkali ions capping the nitride, but their synthesis requires a careful control of the reaction conditions (solvent, temperature, nature of precursor, and alkali ion). The nature of the cation plays an important role in generating a nitride product and results in large structural differences with a bent Th═N═Th moiety found in the K-bound nitride as a result of a strong K-nitride interaction and a linear arrangement in the Cs-bound nitride. Reactivity studies demonstrated the ability of Th nitrides to cleave CO in ambient conditions yielding CN-.

Introduction of plumbole to f-element chemistry.

Herein, we present the synthesis and characterization of heteroleptic lanthanide complexes bearing a dianionic η5-plumbole ligand in their coordination sphere. The reaction proceeds via a salt elimination reaction between the dilithioplumbole ([Li(thf)]2[1,4-bis-tert-butyl-dimethylsilyl-2,3-bis-phenyl-plumbolyl] = [Li2(thf)2(η5-LPb)]) and specifically designed [Ln(η8-COTTIPS)BH4] precursors (Ln = lanthanide, La, Ce, Sm, Er; COTTIPS = 1,4-bis-triisopropylsilyl-cyclooctatetraenyl), that are capable of stabilizing a planar plumbole moiety in the coordination sphere of different trivalent lanthanide ions. In-depth ab initio calculations show that the aromaticity of the dianionic plumbole is retained upon coordination. Electron delocalization occurs from the plumbole HOMO to an orbital of mainly d-character at the lanthanide ion. The magnetic properties of the erbium congener were investigated in detail, leading to the observation of magnetic hysteresis up to 5 K (200 Oe s−1), an unequivocal proof for single molecule magnet behavior in this system. The magnetic behavior of the erbium species can be modulated by manipulating the position of the lithium cation in the complex, which directly influences the bonding metrics in the central [(η5-LPb)Er(η8-COTTIPS)]− fragment. This allowed us to assess a fundamental magneto-structural correlation in an otherwise identical inner coordination sphere.

Functionalized Tris(anilido)triazacyclononanes as Hexadentate Ligands for the Encapsulation of U(III), U(IV) and La(III) Cations

Tripodal multidentate ligands have become increasingly popular in f-element chemistry for stabilizing unusual bonding motifs and supporting small molecule activation processes. The steric and electronic effects of ligand donor atom substituents have proved crucial in both of these applications. In this study we functionalized the previously reported tris-anilide ligand {tacn(SiMe2NPh)3} (tacn = 1,3,7-triazacyclononane) to incorporate substituted aromatic rings, with the aim of modifying f-element complex solubility and ligand steric effects. We report the synthesis of two proligands, {tacn(SiMe2NHAr)3} (Ar = C6H3Me2-3,5 or C6H4Me-4), and their respective group 1 transfer agents—{tacn(SiMe2NKAr)3}, M(III) complexes [M{tacn(SiMe2NAr)3}] for M = La and U, and U(IV) complexes [M{tacn(SiMe2NAr)3}(Cl)]. These compounds were characterized by multinuclear NMR and FTIR spectroscopy and elemental analysis. The paramagnetic uranium complexes were also characterized by solid state magnetic measurements and UV/Vis/NIR spectroscopy. U(III) complexes were additionally studied by EPR spectroscopy. The solid state structures of all f-block complexes were authenticated by single-crystal X-ray diffraction (XRD), together with a minor byproduct [U{tacn(SiMe2NC6H4Me-4)3}(I)]. Comparisons of the characterization data of our f-element complexes with similar literature examples containing the {tacn(SiMe2NPh)3} ligand set showed minor changes in physicochemical properties resulting from the different aromatic ring substitution patterns we investigated.

Uranyl(VI) Triflate as Catalyst for the Meerwein-Ponndorf-Verley Reaction.

Catalytic transformation of oxygenated compounds is challenging in f-element chemistry due to the high oxophilicity of the f-block metals. We report here the first Meerwein-Ponndorf-Verley (MPV) reduction of carbonyl substrates with uranium-based catalysts, in particular from a series of uranyl(VI) compounds where [UO2(OTf)2] (1) displays the greatest efficiency (OTf = trifluoromethanesulfonate). [UO2(OTf)2] reduces a series of aromatic and aliphatic aldehydes and ketones into their corresponding alcohols with moderate to excellent yields, using iPrOH as a solvent and a reductant. The reaction proceeds under mild conditions (80 °C) with an optimized catalytic charge of 2.3 mol % and KOiPr as a cocatalyst. The reduction of aldehydes (1-10 h) is faster than that of ketones (>15 h). NMR investigations clearly evidence the formation of hemiacetal intermediates with aldehydes, while they are not formed with ketones.

Single metal four-electron reduction by U(ii) and masked "U(ii)" compounds.

The redox chemistry of uranium is dominated by single electron transfer reactions while single metal four-electron transfers remain unknown in f-element chemistry. Here we show that the oxo bridged diuranium(iii) complex [K(2.2.2-cryptand)]2[{((Me3Si)2N)3U}2(μ-O)], 1, effects the two-electron reduction of diphenylacetylene and the four-electron reduction of azobenzene through a masked U(ii) intermediate affording a stable metallacyclopropene complex of uranium(iv), [K(2.2.2-cryptand)][U(η2-C2Ph2){N(SiMe3)2}3], 3, and a bis(imido)uranium(vi) complex [K(2.2.2-cryptand)][U(NPh)2{N(SiMe3)2}3], 4, respectively. The same reactivity is observed for the previously reported U(ii) complex [K(2.2.2-cryptand)][U{N(SiMe3)2}3], 2. Computational studies indicate that the four-electron reduction of azobenzene occurs at a single U(ii) centre via two consecutive two-electron transfers and involves the formation of a U(iv) hydrazide intermediate. The isolation of the cis-hydrazide intermediate [K(2.2.2-cryptand)][U(N2Ph2){N(SiMe3)2}3], 5, corroborated the mechanism proposed for the formation of the U(vi) bis(imido) complex. The reduction of azobenzene by U(ii) provided the first example of a “clear-cut” single metal four-electron transfer in f-element chemistry.

Stabilization of Plutonium(V) Within a Crown Ether Inclusion Complex

Crystalline coordination complexes of actinides, especially in atypical oxidation states, are not only fundamentally important for expanding the notably limited knowledge on the bonding nature of a...

F-Orbital Mixing in the Octahedral f2 Compounds UX62- [X = F, Br, Cl, I] and PrCl63.

Understanding how interactions between the f orbitals and ligand orbitals in lanthanide and actinide systems affect their physical properties is the central issue in f-element chemistry. A wide variety of approaches including both theoretical and experimental tools have been used to study these relationships. Among the most widely used tools has been crystal field theory (CFT), which bridges theory and experiment in that it is a model based largely on atomic theory that is parametrized using experimental data. Crystal field theory is quite accurate for the lanthanides, due in part to the highly contracted nature of the 4f orbitals. For actinides, crystal field theory is less accurate, potentially due to the treatment of orbital mixing. In CFT, orbital mixing is handled implicitly by allowing the electron repulsion parameters (Slater Fk parameters) and the spin-orbit coupling constant to vary. As a result, orbital mixing in CFT is isotropic in that the Fk parameters and the spin-orbit coupling constant affect all f orbitals equally. This approximation works well for the lanthanides due to the limited degree of orbital mixing in these complexes. In actinide complexes, the 5f orbitals have greater overlap with the ligand orbitals, and this approximation is less accurate than in the lanthanides. Here, we report a modification of CFT that includes the effect of orbital mixing on electron repulsion and spin-orbit coupling for each f orbital. The model is applied to the tetravalent uranium hexahalide dianions and PrCl63- for which the energies of many low-lying excited states are known. The new model generally fits the data as well the traditional CFT although with fewer parameters. However, the new model does not fit the data better than the more complex CFT models of Faucher and co-workers. The results of the model show in detail how changes in overlap and orbital energies influence the energies of the bonding and antibonding orbitals.

Chasing Multiple Bonding Interactions between Alkaline-Earth Metals and Main-Group Fragments.

Formally dianionic ligands such as alkylidenes or organoimidos play a major role in the organometallic chemistry of transition metals and are an emerging topical area of f-element chemistry. The pursuit and development of main-group-metal congeners has been tackled sporadically but is clearly lacking behind. The pronounced ionic bonding in particular, prevailing in alkali and alkaline-earth (Ae) metal derivatives, proved cumbersome. Recent substantial progress in the respective field of divalent Ae chemistry has been triggered by the implementation of new synthesis strategies involving new AeII precursors and tailor-made ligands. The main emphasis of this Minireview will be on the synthesis and reactivity of well-defined Group 2 alkylidenes, organoimides, silylenes, and phosphandiides.

Samarium Polyarsenides Derived from Nanoscale Arsenic.

Zintl phases of arsenic and molecular compounds containing Zintl-type polyarsenide ions are of fundamental interest in basic and applied sciences. Unfortunately, the most obvious and reactive arsenic source for the preparation of defined molecular polyarsenide compounds, yellow arsenic As4 , is very inconvenient to prepare and neither storable in pure form nor easy to handle. Herein, we present the synthesis and reactivity of elemental As0 nanoparticles (As0 Nano , d=7.2±1.8 nm), which were successfully utilized as a reactive arsenic source in reductive f-element chemistry. Starting from [Cp*2 Sm] (Cp*=η5 -C5 Me5 ), the samarium polyarsenide complexes [(Cp*2 Sm)2 (μ-η2 :η2 -As2 )] and [(Cp*2 Sm)4 As8 ] were obtained from As0 nano , thereby generating the largest molecular polyarsenide of the f-elements and circumventing the use of As4 in preparative chemistry.

Catalyst: Nuclear Power in the 21st Century

Download : Download full-size image Profs. Nik Kaltsoyannis and Steve Liddle joined the University of Manchester School of Chemistry in 2015 as co-directors of the Centre for Radiochemistry Research after having previously held chairs at, respectively, University College London and the University of Nottingham. They are also heads of computational and inorganic chemistry, respectively. Each has published ∼150 research articles, reviews, and book chapters and has extensive experience in f-element chemistry. Prof. Kaltsoyannis co-leads the PuO2 work package of the Engineering and Physical Sciences Research Council’s (EPSRC’s) “DISTINCTIVE” nuclear-waste decommissioning consortium. Prof. Liddle holds an EPSRC Established Career Fellowship and is a vice president of the European Rare Earth and Actinide Society.

Reaction: Recycling and Generation IV Systems

Dame Sue Ion is chair of the UK Nuclear Innovation Research Advisory Board. She represents the UK on a number of international review and oversight committees for the nuclear sector, including the Euratom Science and Technology Committee, which she chairs. She is the only non-US member of the US Department of Energy's Nuclear Energy Advisory Committee, on which she has served since 2005.

ChemInform Abstract: C‐F→Ln/An Interactions in Synthetic F‐Element Chemistry

AbstractReview: 80 refs.

Nucleophilic Reactivity of a Nitride-Bridged Diuranium(IV) Complex: CO2 and CS2 Functionalization.

Thermolysis of the nitride-bridged diuranium(IV) complex Cs{(μ-N)[U(OSi(O(t) Bu)3)3]2} (1) showed that the bridging nitride behaves as a strong nucleophile, promoting N-C bond formation by siloxide ligand fragmentation to yield an imido-bridged siloxide/silanediolate diuranium(IV) complex, Cs{(μ-N(t) Bu)(μ-O2 Si(O(t) Bu)2)U2 (OSi(O(t) Bu)3)5}. Complex 1 displayed reactivity towards CS2 and CO2 at room temperature that is unprecedented in f-element chemistry, affording diverse N-functionalized products depending on the reaction stoichiometry. The reaction of 1 with two equivalents of CS2 yielded the thiocyanate/thiocarbonate complex Cs{(μ-NCS)(μ-CS3 )[U(OSi(O(t)Bu)3)3]2} via a putative NCS(-)/S(2-) intermediate. The reaction of 1 with one equivalent of CO2 resulted in deoxygenation and N-C bond formation, yielding the cyanate/oxo complex Cs{(μ-NCO)(μ-O)[U(OSi(O(t) Bu)3 )3]2}. Addition of excess CO2 to 1 led to the unprecedented dicarbamate product Cs{(μ-NC2O4)[U(OSi(O(t) Bu)3)3]2}.

C-F→Ln/An interactions in synthetic f-element chemistry.

The coordination of C-F moieties to electrophilic metal cations has been increasingly recognized in f-element chemistry over the last two decades. These C-F→Ln/An interactions are readily identified in the solid state and can persist in solution. The binding energies of C-F→Ln/An interactions lead to their ready displacement to expose metal centers to substrates, which is implicated in cationic polymerization catalysts. C-F→Ln/An coordination is also an elementary step in C-F bond activation, proceeding through either homolytic or heterolytic cleavage of chemically inert C-F bonds. The influence of C-F→Ln/An interactions on the geometries of coordination compounds and their electronic impact on metal cations are also examined in this Perspective article.

Isolation of Uranyl Dicyanamide Complexes from N-Donor Ionic Liquids.

An ionic liquid (IL) approach for soft-donor f-element chemistry has been demonstrated by the isolation of several new uranyl dicyanamide complexes through reactions of UO2(NO3)2·6H2O with dicyanamide ([N(CN)2](-))-containing ILs. The [N(CN)2](-) ions are able to rapidly substitute uranium's O-donor ligands, as evidenced by single-crystal X-ray diffraction studies on two anhydrous adducts of UO2(NO3)2 with [N(CN)2](-) ILs as well as by IR and NMR spectroscopic studies on solutions of UO2(NO3)2 in these ILs. By contrast, the slow reaction of UO2(OAc)2·2H2O with a nitrile-functionalized imidazolium dicyanamide IL in solvent and the reaction of UO2(NO3)2·6H2O with NaN(CN)2 at elevated temperature resulted in irreversible hydrolysis. The reaction of UO2SO4 with [N(CN)2](-) ions in an acidified aqueous solution resulted in the crystallization of a [UO2](2+) complex with biuret, a N(CN)2](-) hydrolysis product. [N(CN)2](-) ions in the form of ILs react rapidly with [UO2](2+) at room temperature, allowing ligand substitution with [N(CN)2](-) to out-compete the slower hydrolysis reaction, enabling the isolation of uranyl dicyanamide complexes and challenging assumptions regarding the affinity of uranium for O-donors.

Even and odd: uranium(IV) complexes with two, four, and six salicylaldiminate ligands with an unusual κ1-coordination mode

We report the synthesis and structural determination of three uranium(IV) complexes bearing two, four, and six salicylaldiminate ligands. Reaction of UI4(1,4-dioxane)2 with two, four, and six equivalents of K[OC6H4C(H)=N(2,6-iPr2C6H3)], 1, yielded [(2,6-iPr2C6H3)N=C(H)C6H4O-κ2(O,N)]2UI2(NCCH3), 2, [(2,6-iPr2C6H3)N=C(H)C6H4O-κ1(O)]2[(2,6-iPr2C6H3)N=C(H)C6H4O-κ2(O,N)]2U(THF), 3, and {[2,6-iPr2C6H3)N=C(H)C6H4O-κ1(O)]6U}2−, 4. While 2 shows normal κ2-coordination through both oxygen and nitrogen donors, 3 has two salicylaldiminate ligands bound only through oxygen and 4 has all six ligands bound only through oxygen. This is an exceedingly rare example of a chelating ligand not completing its chelation in f-element chemistry. In addition, 4 is the first report of a homoleptic octahedral actinide complex with a Schiff base ligand.

Can a pentamethylcyclopentadienyl ligand act as a proton-relay in f-element chemistry? Insights from a joint experimental/theoretical study.

Isomerisation of buta-1,2-diene to but-2-yne by (Me(5)C(5))(2)Yb is a thermodynamically favourable reaction, with the Δ(r)G° estimated from experimental data at 298 K to be -3.0 kcal mol(-1). It proceeds in hydrocarbon solvents with a pseudo first-order rate constant of 6.4 × 10(-6) s(-1) and 7.4 × 10(-5) s(-1) in C(6)D(12) and C(6)D(6), respectively, at 20 °C. This 1,3-hydrogen shift is formally forbidden by symmetry and has to occur by an alternative pathway. The proposed mechanism for buta-1,2-diene to but-2-yne isomerisation by (Me(5)C(5))(2)Yb involves coordination of methylallene (buta-1,2-diene) to (Me(5)C(5))(2)Yb, and deprotonation of methylallene by one of the Me(5)C(5) ligands followed by protonation of the terminal methylallenyl carbon to yield the known coordination compound (Me(5)C(5))(2)Yb(η(2)-MeC[triple bond, length as m-dash]CMe). Computationally, this mechanism is not initiated by a single electron transfer step, and the ytterbium retains its oxidation state (II) throughout the reactivity. Experimentally, the influence of the metal centre is discussed by comparison with the reaction of (Me(5)C(5))(2)Ca towards buta-1,2-diene, and (Me(5)C(5))(2)Yb with ethylene. The mechanism by which the Me(5)C(5) acts as a proton-relay within the coordination sphere of a metal also rationalises the reactivity of (i) (Me(5)C(5))(2)Eu(OEt(2)) with phenylacetylene, (ii) (Me(5)C(5))(2)Yb(OEt(2)) with phenylphosphine and (iii) (Me(5)C(5))(2)U(NPh)(2) with H(2) to yield (Me(5)C(5))(2)U(HNPh)(2). In the latter case, the computed mechanism is the heterolytic activation of H(2) by (Me(5)C(5))(2)U(NPh)(2) to yield (Me(5)C(5))(2)U(H)(HNPh)(NPh), followed by a hydrogen transfer from uranium back to the imido nitrogen atom using one Me(5)C(5) ligand as a proton-relay. The overall mechanism by which hydrogen shifts using a pentamethylcyclopentadienyl ligand as a proton-relay is named Carambole in reference to carom billiards.

Thermodynamic Features of Benzene-1,2-Diphosphonic Acid Complexes with Several Metal Ions

Among his many contributions to the advancement of f-element chemistry and separation science, Professor Gregory R. Choppin's research group completed numerous investigations featuring the application of distribution techniques to the determination of metal complexation equilibrium quotients. Most of these studies focused on the chemistry of lanthanide and actinide complexes. In keeping with that tradition, this report discusses the complex formation equilibrium constants for complexes of trivalent europium (Eu3+) with benzene-1,2-diphosphonic acid (H4BzDP) determined using solvent extraction distribution experiments in 0.2 M (Na,H)ClO4 media in the temperature range of 5 – 45°C. Protonation constants for HnBzDP4-n and stoichiometry and stability of BzDP4- complexes with Zn2+, Ni2+, and Cu2+ have also been determined using potentiometric titration (at I = 0.1 M) and 31P NMR spectroscopy. Heats of protonation of HnBzDPn-4 species have been determined by titration calorimetry. From the temperature dependence of the complex Eu3+-HnBzDPn-4 equilibrium constant, a composite enthalpy (ΔH = −15.1 (±1.0) kJ mol−1) of complexation has been computed. Comparing these thermodynamic parameters with literature reports on other diphosphonic acids and structurally similar carboxylic acids indicates that exothermic heats of complexation are unique to the Eu-BzDP system. Comparisons with thermodynamic data from the literature indicate that the fixed geometry imposed by the benzene ring enhances complex stability.