Themed collection New molecules and materials from the f-block
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Small molecule activation by multimetallic uranium complexes supported by siloxide ligands
An overview of the small molecule activation chemistry of polynuclear complexes of uranium supported by the tert-butoxysiloxide ligand.
Chem. Commun., 2019,55, 13031-13047
https://doi.org/10.1039/C9CC05605J
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Lanthanide-based tools for the investigation of cellular environments
Coordination complexes and supramolecules based on trivalent lanthanides for probing biological systems, in particular intracellular environments, are reviewed.
Chem. Commun., 2018,54, 10021-10035
https://doi.org/10.1039/C8CC05271A
Steric vs. electronic stereocontrol in syndio- or iso-selective ROP of functional chiral β-lactones mediated by achiral yttrium-bisphenolate complexes
Electronic vs. steric effects of ligand ortho-substituents in (bis)phenolate yttrium-based complexes for preparation of a large scope of stereoregular poly(3-hydroxyalkanoate)s.
Chem. Commun., 2018,54, 8024-8031
https://doi.org/10.1039/C8CC03842B
Electrochemical oxidation of trivalent americium using a dipyrazinylpyridine modified ITO electrode
We present here the electrochemical oxidation of Am(III) to AmVO2+ and AmVIO22+ in pH 1 nitric acid using a mesoporous tin-doped indium oxide electrode modified with a covalently attached dipyrazinylpyridine ligand.
Chem. Commun., 2019,55, 4035-4038
https://doi.org/10.1039/C9CC00837C
Soft-donor dipicolinamide derivatives for selective actinide(III)/lanthanide(III) separation: the role of S- vs. O-donor sites
A dithiopicolinamide analog selectively extracts Am(III) over Eu(III) under acidic conditions.
Chem. Commun., 2019,55, 2441-2444
https://doi.org/10.1039/C8CC07683A
Moderate supercritical synthesis as a facile route to mixed-valent uranium(IV,V) and (V,VI) silicates
The synthesis of five new U(IV,V) and U(V,VI) silicates points toward moderate supercritical synthesis as a new route to the stabilization of mixed-valent uranium compounds.
Chem. Commun., 2018,54, 13794-13797
https://doi.org/10.1039/C8CC07789D
Actinide-transition metal bonding in heterobimetallic uranium– and thorium–molybdenum paddlewheel complexes
Heterobimetallic An–Mo (An = U, Th) paddlewheel complexes featuring dative Mo → An bonds are reported.
Chem. Commun., 2018,54, 13515-13518
https://doi.org/10.1039/C8CC05268A
Ca(II), Yb(II) and Tm(III) complexes with tri- and tetra-anions of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene
Sandwich-like structures derived from organic polyanions and multi-centered cation assemblies.
Chem. Commun., 2018,54, 12950-12953
https://doi.org/10.1039/C8CC08108E
Single crystal growth and magnetic properties of the mixed valent Yb containing Zintl phase, Yb14MgSb11
Large crystals of Yb14MgSb11 prepared by Sn flux show the presence of Yb3+ making this compound a Zintl phase.
Chem. Commun., 2018,54, 12946-12949
https://doi.org/10.1039/C8CC05471A
Exploring the electronic structure and speciation of aqueous and colloidal Pu with high energy resolution XANES and computations
Pu L3 HR-XANES fingerprints loss of inversion symmetry: rising pre-edge (d,e), shorter A–B distance (d,e), split Pu d-DOS (e).
Chem. Commun., 2018,54, 12824-12827
https://doi.org/10.1039/C8CC06889E
Plutonium coordination and redox chemistry with the CyMe4-BTPhen polydentate N-donor extractant ligand
Complexation of Pu(IV) with the actinide extractant CyMe4-BTPhen (2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-1,10-phenanthroline) was studied experimentally and by computational analysis.
Chem. Commun., 2018,54, 12582-12585
https://doi.org/10.1039/C8CC06015K
The electronic structure of f-element Prussian blue analogs determined by soft X-ray absorption spectroscopy
Isomorphous lanthanides and actinides Prussian blue analogs showing distinct optical and vibrational properties are studied using nitrogen K edge and iron K edge.
Chem. Commun., 2018,54, 12206-12209
https://doi.org/10.1039/C8CC05176C
Organosoluble tetravalent actinide di- and trifluorides
Soluble molecular actinide(IV) fluorides can be prepared in high yield via redox or metathesis reactions of silver fluorides with actinide compounds containing ancillary iodide or fluorinated thiolate ligands.
Chem. Commun., 2018,54, 12018-12020
https://doi.org/10.1039/C8CC05501G
Plutonium chlorido nitrato complexes: ligand competition and computational metrics for assembly and bonding
Four novel Pu(IV) nitrato chloro complexes were crystallographically characterized and the Pu–ligand bond nature was delineated computationally.
Chem. Commun., 2018,54, 12014-12017
https://doi.org/10.1039/C8CC05578E
Stereo-selectivity switchable ROP of rac-β-butyrolactone initiated by salan-ligated rare-earth metal amide complexes: the key role of the substituents on ligand frameworks
A series of novel salan-ligated rare-earth metal amide complexes were prepared and employed as initiators for the ROP of rac-β-butyrolactone (rac-BBL).
Chem. Commun., 2018,54, 11998-12001
https://doi.org/10.1039/C8CC05469J
Polyethyleneimine methylenecarboxylate: a macromolecular DTPA analogue to chelate plutonium(IV)
Polyethyleneimine methylenecarboxylate (PEI-MC) is explored as a possible new class of macromolecular decorporation agents in case of plutonium contamination.
Chem. Commun., 2018,54, 11705-11708
https://doi.org/10.1039/C8CC05206A
Solid-state structural elucidation and electrochemical analysis of uranyl naphthylsalophen
The synthesis, characterization, and electrochemical properties of a napthylsalophen and its uranyl (UO22+) complex are described.
Chem. Commun., 2018,54, 11693-11696
https://doi.org/10.1039/C8CC05242E
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The semiquinone radical anion of 1,10-phenanthroline-5,6-dione: synthesis and rare earth coordination chemistry
The redox-active ligand as a route to heterobimetallic rare earth-transition metal compounds containing a semiquinone radical anion.
Chem. Commun., 2018,54, 11284-11287
https://doi.org/10.1039/C8CC05591B
Molecular hydrides of divalent ytterbium supported by a macrocyclic ligand: synthesis, structure and olefin hydrofunctionalization catalysis
Cationic ytterbium hydrides [(Me4TACD)2Yb2H(2+n)](2−n)+ (n = 0, 1) catalyzed the H2/D2 isotope exchange as well as hydrogenation and hydrosilylation of 1-hexene.
Chem. Commun., 2018,54, 11280-11283
https://doi.org/10.1039/C8CC05152F
Post Hartree–Fock calculations of pnictogen–uranium bonding in EUF3 (E = N–Bi)
CASSCF and CASPT2 calculations are reported on EUF3 (E = N, P, As, Sb, Bi), emphasising the influence of the size of the active space on the E–U bond.
Chem. Commun., 2018,54, 11100-11103
https://doi.org/10.1039/C8CC05581E
Catalytic regeneration of a Th–H bond from a Th–O bond through a mild and chemoselective carbonyl hydroboration
Organoactinide-mediated chemoselective hydroboration of aldehydes and ketones. The catalytic regeneration of a Th–H bond from a Th–OR bond was achieved via hydroboration with HBpin.
Chem. Commun., 2018,54, 11001-11004
https://doi.org/10.1039/C8CC05030A
Two-electron oxidation of a homoleptic U(III) guanidinate complex by diphenyldiazomethane
Use of a new homoleptic U(III) tris-guanidinate system stabilizes the formation of the first U(V) hydrazido complex.
Chem. Commun., 2018,54, 10913-10916
https://doi.org/10.1039/C8CC06514D
Towards understanding of lanthanide–transition metal bonding: investigations of the first Ce–Fe bonded complex
The syntheses, structural, and magnetic characterization of three new organometallic Ce complexes stabilized by PyCp22− (PyCp22− = [2,6-(CH2C5H3)2C5H3N]2−) are reported.
Chem. Commun., 2018,54, 10893-10896
https://doi.org/10.1039/C8CC05243C
Impacts of oxo interactions within actinyl metal organic materials: highlight on thermal expansion behaviour
Interactions between H-donors and U(VI) and Np(V) oxo groups impact the thermal expansion properties of materials.
Chem. Commun., 2018,54, 10828-10831
https://doi.org/10.1039/C8CC05240A
Reductive activation of neptunyl and plutonyl oxo species with a hydroxypyridinone chelating ligand
Neptunyl(VI) and plutonyl(VI) oxo-activation with reduction to tetravalent hydroxides was investigated in gas and condensed phases, and by density functional theory.
Chem. Commun., 2018,54, 10698-10701
https://doi.org/10.1039/C8CC05626A
Spiral Eu(III) coordination polymers with circularly polarized luminescence
A spiral-type chiral Eu(III) coordination polymer showed strong luminescence, effective CD and CPL properties compared with a mono-nuclear chiral Eu(III) complex in the solid state.
Chem. Commun., 2018,54, 10695-10697
https://doi.org/10.1039/C8CC05147J
Revisiting complexation thermodynamics of transplutonium elements up to einsteinium
In contrast with previous literature, this report notes einsteium's chemistry is a continuation of the earlier actinide series.
Chem. Commun., 2018,54, 10578-10581
https://doi.org/10.1039/C8CC05230A
Structure and properties of [(4,6-tBu2C6H2O)2Se]2An(THF)2, An = U, Np, and their reaction with p-benzoquinone
The synthesis and characterization of U(IV) and Np(IV) selenium bis(phenolate) complexes are reported.
Chem. Commun., 2018,54, 10435-10438
https://doi.org/10.1039/C8CC05244A
Photochemical and electrochemical hydrogen evolution reactivity of lanthanide-functionalized polyoxotungstates
The first example of molecular lanthanide tungstate clusters for photochemical and electrochemical hydrogen evolution catalysis is reported.
Chem. Commun., 2018,54, 10427-10430
https://doi.org/10.1039/C8CC06334F
Modelling uranyl chemistry in liquid ammonia from density functional theory
We developed a computationally-efficient protocol based on Density Functional Theory (DFT) and a continuum solvation model (CSM) to predict reaction free energies of complexation reactions of uranyl in liquid ammonia.
Chem. Commun., 2018,54, 10431-10434
https://doi.org/10.1039/C8CC05382K
The “Wanderlust” of Me3Si groups in rare-earth triple-decker complexes: a combined experimental and computational study
The migration of Me3Si groups (“Wanderlust”) in rare-earth triple-decker sandwich complexes of the type Ln2(COT′′)3 (COT′′ = bis(trimethylsilyl)cyclooctatetraenyl) has been elucidated by a combined experimental and computational study.
Chem. Commun., 2018,54, 10280-10283
https://doi.org/10.1039/C8CC05317K
Synthesis of uranium-in-cryptand complexes
Uranium-in-cryptand complexes can be readily synthesized by reacting UI3 with 2.2.2-cryptand.
Chem. Commun., 2018,54, 10272-10275
https://doi.org/10.1039/C8CC05341C
A tetranuclear samarium(II) inverse sandwich from direct reduction of toluene by a samarium(II) siloxide
The dinuclear SmII complex [Sm2L4(dme)] (L = OSi(OtBu)3) reacts slowly with toluene, resulting in the isolation of the triple decker arene-bridged SmII complex [{Sm2L3}2(μ-η6:η6-C7H8)] in 44% yield. This reactivity provides the first example of an unambiguous arene reduction by an isolated SmII species.
Chem. Commun., 2018,54, 10268-10271
https://doi.org/10.1039/C8CC04169E
A molecular basis to rare earth separations for recycling: tuning the TriNOx ligand properties for improved performance
A methoxy-substituted tripodal hydroxylamine ligand, H3TriNOxOMe, was synthesized and coordinated to rare earth cations for separation purposes.
Chem. Commun., 2018,54, 10276-10279
https://doi.org/10.1039/C8CC04409K
Exploring the intramolecular catalysis of the proton exchange process to modulate the relaxivity of Gd(III)-complexes of HP-DO3A-like ligands
The GdIII complex of Ph-HP-DO3A shows the highest contribution to the relaxivity by the intramolecular proton exchange of the –OH group.
Chem. Commun., 2018,54, 10056-10059
https://doi.org/10.1039/C8CC05284K
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{Np38} clusters: the missing link in the largest poly-oxo cluster series of tetravalent actinides
The poly-oxo clusters of neptunium, {Np38}, fill the gap in the largest poly-oxo cluster series of tetravalent actinides.
Chem. Commun., 2018,54, 10060-10063
https://doi.org/10.1039/C8CC03744B
Square supramolecular assemblies of uranyl complexes in organic solvents
Uranyl, ligand and solvent interactions lead to unique supramolecular assembly.
Chem. Commun., 2018,54, 10064-10067
https://doi.org/10.1039/C8CC05277H
Trends in the valence band electronic structures of mixed uranium oxides
The valence band electronic structures of mixed uranium oxides (UO2, U4O9, U3O7, U3O8, and β-UO3) have been studied using the resonant inelastic X-ray scattering (RIXS) technique at the U M5 edge and computational methods.
Chem. Commun., 2018,54, 9757-9760
https://doi.org/10.1039/C8CC05464A
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Elucidation of the inverse trans influence in uranyl and its imido and carbene analogues via quantum chemical simulation
The inverse trans influence is quantified in uranyl and its analogues via analysis of quantum chemically-derived electron density distributions.
Chem. Commun., 2018,54, 9761-9764
https://doi.org/10.1039/C8CC06088F
Uranyl dication mediated photoswitching of a calix[4]pyrrole-based metal coordination cage
A set of self-assembled tri- and tetrapodal metal coordination cage structures (cage-1 and cage-2, respectively) constructed from the uranyl dication (UO22+) and a dibenzoic acid functionalised cis-calix[4]pyrrole (1) are described.
Chem. Commun., 2018,54, 9422-9425
https://doi.org/10.1039/C8CC05160G
Terbocenium: completing a heavy lanthanide metallocenium cation family with an alternative anion abstraction strategy
A series of lanthanide metallocenium cations [Ln(Cpttt)2]+ (Ln = Y, Gd, Dy, Ho, Er, Tm, Yb, Lu; Cpttt = C5H2tBu3-1,2,4) were recently prepared, but curiously the Tb analogue was elusive. Here we access [Tb(Cpttt)2]+via an alternative strategy, completing the heavy [Ln(Cpttt)2]+ family.
Chem. Commun., 2018,54, 9182-9185
https://doi.org/10.1039/C8CC05261A
Activation of carbon suboxide (C3O2) by U(III) to form a cyclobutane-1,3-dione ring
[U(η5-C5H4SiMe3)3] reductively couples three C3O2 molecules to form a tetranuclear complex with a central cyclobutane-1,3-dione ring, via an intermediate bridging ketene complex.
Chem. Commun., 2018,54, 8830-8833
https://doi.org/10.1039/C8CC04391D
Synthesis of homometallic divalent lanthanide organoimides from benzyl complexes
Double protonolysis of [Ln(CH2Ph)2]n (Ln = Eu and Yb) with 2,6-diisopropylaniline gives efficient access to [(thf)Ln(μ3-NDipp)]4 featuring a heterocubane structure.
Chem. Commun., 2018,54, 8826-8829
https://doi.org/10.1039/C8CC05234D
Schiff-base coordination complexes with plutonium(IV) and cerium(IV)
The synthesis and characterization of a Pu(IV) salen complex reveals the stabilization of the +4 oxidation state with respect to that observed with Ce(IV).
Chem. Commun., 2018,54, 8634-8636
https://doi.org/10.1039/C8CC03571G
Yet again, new compounds found in systems with known binary phase diagrams. Synthesis, crystal and electronic structure of Nd3Bi7 and Sm3Bi7
Reported, for the very first time, are the synthesis and structures of two new compounds, discovered in well-studied binary phase diagrams.
Chem. Commun., 2018,54, 7089-7092
https://doi.org/10.1039/C8CC02563K
Single-molecule magnet properties of a monometallic dysprosium pentalene complex
The pentalene-ligated dysprosium complex [(η8-Pn†)Dy(Cp*)] (1Dy) (Pn† = [1,4-(iPr3Si)2C8H4]2−) and its magnetically dilute analogue are single-molecule magnets, with energy barriers of 245 cm−1.
Chem. Commun., 2018,54, 7085-7088
https://doi.org/10.1039/C8CC03516D
Synthesis and structural characterization of the first neptunium based metal–organic frameworks incorporating {Np6O8} hexanuclear clusters
The synthesis of the first transuranium Metal–Organic Frameworks (TRU-MOFs) is reported here.
Chem. Commun., 2018,54, 6979-6982
https://doi.org/10.1039/C8CC03121E
Homoleptic uranium and lanthanide phosphinodiboranates
The synthesis and structures of a new class of homoleptic f-metal borohydride complexes (phosphinodiboranates) are described with U, Nd, and Er.
Chem. Commun., 2018,54, 5602-5605
https://doi.org/10.1039/C8CC02862A
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Double uranium oxo cations derived from uranyl by borane or silane reduction
A new type of double uranium oxo cation [O–U–O–U–O]4+ is prepared by selective oxygen-atom abstraction from macrocyclic uranyl complexes using either boranes or silanes.
Chem. Commun., 2018,54, 3839-3842
https://doi.org/10.1039/C8CC00341F