Special Issue "Rare Earth and Actinide Complexes"

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: closed (31 December 2015)

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A printed edition of this Special Issue is available here.

Special Issue Editors

Guest Editor
Dr. Stephen Mansell

School of Engineering & Physical Sciences; Chemical Sciences,Heriot-Watt University, UK
Website | E-Mail
Guest Editor
Prof. Dr. Steve Liddle

School of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK
Website | E-Mail
Phone: +0161-275-4612
Interests: f-block chemistry; metal-metal bonding; metal-ligand multiple bonding; small molecule activation; single molecule magnetism

Special Issue Information

Dear Colleagues,

As the fields of organometallic and coordination chemistry of the transition metals has grown more mature, the under-explored chemistry of the rare-earths and actinides has drawn the attention of research groups from across the globe looking for new fundamental discoveries and access to compounds with unique properties. The rare earths – the group 3 metals and the 4f lanthanide series – have long shown many interesting properties in the solid state which exploit their unique electronic configurations. However, it is the molecular chemistry of these metals that has expanded dramatically in recent years as researchers identify the differences between – and unique features of – their molecular compounds. Recent highlights include the identification of new oxidation states and patterns of reactivity as well as applications in medical imaging and health care which represent new and exciting areas of research. The actinides show a wide range of different properties as a consequence of their radioactivity and radiochemistry, but this has not stopped recent rapid progress into the exploration of their unique chemistry. Uranium, in particular, shows huge potential with its transition metal like range of oxidation states (+2 to +6), and in specialised laboratories, the heavier actinides are also beginning to show their unique chemistry as well. This Special Issue aims to bring together these strands of research in an openly-accessible way to allow better communication of these advances to a wider audience. This is necessary as despite these exciting advances, the rare earths and actinides are still much neglected topics in both school and undergraduate curriculums. Therefore, we invite you to contribute papers in the above mentioned areas and allow your research to inform and influence the next generation of scientist to keep the field as vibrant as it is today.

Dr Stephen Mansell
Prof. Dr. Steve Liddle
Guest Editors

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Keywords

  • Organometallic chemistry
  • Reactivity
  • Catalysis
  • Theoretical studies
  • Health and medical applications
  • Electronic and magnetic properties
  • Environmental aspects
  • Understanding products generated in the nuclear industry

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Published Papers (17 papers)

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Editorial

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Open AccessEditorial Rare Earth and Actinide Complexes
Inorganics 2016, 4(4), 31; doi:10.3390/inorganics4040031
Received: 4 October 2016 / Revised: 10 October 2016 / Accepted: 12 October 2016 / Published: 14 October 2016
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Abstract
The rare earth metals (scandium, yttrium, lanthanum and the subsequent 4f elements) and actinides (actinium and the 5f elements) are vital components of our technology-dominated society.[...] Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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Research

Jump to: Editorial, Review

Open AccessArticle Optical Properties of Heavily Fluorinated Lanthanide Tris β-Diketonate Phosphine Oxide Adducts
Inorganics 2016, 4(3), 27; doi:10.3390/inorganics4030027
Received: 13 June 2016 / Revised: 27 July 2016 / Accepted: 9 August 2016 / Published: 20 September 2016
Cited by 1 | PDF Full-text (1967 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The construction of lanthanide(III) chelates that exhibit superior photophysical properties holds great importance in biological and materials science. One strategy to increase the luminescence properties of lanthanide(III) chelates is to hinder competitive non-radiative decay processes through perfluorination of the chelating ligands. Here, the
[...] Read more.
The construction of lanthanide(III) chelates that exhibit superior photophysical properties holds great importance in biological and materials science. One strategy to increase the luminescence properties of lanthanide(III) chelates is to hinder competitive non-radiative decay processes through perfluorination of the chelating ligands. Here, the synthesis of two families of heavily fluorinated lanthanide(III) β-diketonate complexes bearing monodentate perfluorinated tris phenyl phosphine oxide ligands have been prepared through a facile one pot reaction [Ln(hfac)3{(ArF)3PO}(H2O)] and [Ln(F7-acac)3{(ArF)3PO}2] (where Ln = Sm3+, Eu3+, Tb3+, Er3+ and Yb3+). Single crystal X-ray diffraction analysis in combination with photophysical studies have been performed to investigate the factors responsible for the differences in the luminescence lifetimes and intrinsic quantum yields of the complexes. Replacement of both bound H2O and C–H oscillators in the ligand backbone has a dramatic effect on the photophysical properties of the complexes, particularly for the near infra-red emitting ion Yb3+, where a five fold increase in luminescence lifetime and quantum yield is observed. The complexes [Sm(hfac)3{(ArF)3PO}(H2O)] (1), [Yb(hfac)3{(ArF)3PO}(H2O)] (5), [Sm(F7-acac)3{(ArF)3PO}2] (6) and [Yb(F7-acac)3{(ArF)3PO}2] (10) exhibit unusually long luminescence lifetimes and attractive intrinsic quantum yields of emission in fluid solution (ΦLn = 3.4% (1); 1.4% (10)) and in the solid state (ΦLn = 8.5% (1); 2.0% (5); 26% (6); 11% (10)), which are amongst the largest values for this class of compounds to date. Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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Open AccessArticle A Structural and Spectroscopic Study of the First Uranyl Selenocyanate, [Et4N]3[UO2(NCSe)5]
Inorganics 2016, 4(1), 4; doi:10.3390/inorganics4010004
Received: 30 October 2015 / Revised: 27 January 2016 / Accepted: 4 February 2016 / Published: 16 February 2016
Cited by 4 | PDF Full-text (1847 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The first example of a uranyl selenocyanate compound is reported. The compound [Et4N]3[UO2(NCSe)5] has been synthesized and fully characterized by vibrational and multinuclear (1H, 13C{1H} and 77Se{1H})
[...] Read more.
The first example of a uranyl selenocyanate compound is reported. The compound [Et4N]3[UO2(NCSe)5] has been synthesized and fully characterized by vibrational and multinuclear (1H, 13C{1H} and 77Se{1H}) NMR spectroscopy. The photophysical properties have also been recorded and trends in a series of uranyl pseudohalides discussed. Spectroscopic evidence shows that the U–NCSe bonding is principally ionic. An electrochemical study revealed that the reduced uranyl(V) species is unstable to disproportionation and a ligand based oxidation is also observed. The structure of [Et4N]4[UO2(NCSe)5][NCSe] is also presented and Se···H–C hydrogen bonding and Se···Se chalcogen–chalcogen interactions are seen. Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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Open AccessArticle Tuning of Hula-Hoop Coordination Geometry in a Dy Dimer
Inorganics 2016, 4(1), 2; doi:10.3390/inorganics4010002
Received: 18 September 2015 / Revised: 22 December 2015 / Accepted: 31 December 2015 / Published: 8 January 2016
Cited by 1 | PDF Full-text (1943 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The reaction of DyCl3 with hydrazone Schiff base ligands and sodium acetate in the presence of triethylamine (Et3N) as base affords two dysprosium dimers: [Dy2(HL1)2(OAc)2(EtOH)(MeOH)] (1) and [Dy2(L2)2(OAc)
[...] Read more.
The reaction of DyCl3 with hydrazone Schiff base ligands and sodium acetate in the presence of triethylamine (Et3N) as base affords two dysprosium dimers: [Dy2(HL1)2(OAc)2(EtOH)(MeOH)] (1) and [Dy2(L2)2(OAc)2(H2O)2]·2MeOH (2). The DyIII ions in complexes 1 and 2 are linked by alkoxo bridges, and display “hula hoop” coordination geometries. Consequently, these two compounds show distinct magnetic properties. Complex 1 behaves as a field-induced single molecule magnet (SMM), while typical SMM behavior was observed for complex 2. In addition, comparison of the structural parameters among similar Dy2 SMMs with hula hoop-like geometry reveals the significant role played by coordination geometry and magnetic interaction in modulating the relaxation dynamics of SMMs. Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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Open AccessArticle Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C5Me4R)2UBr2, (C5Me4R)2U(O-2,6-iPr2C6H3)(Br), and [K(THF)][(C5Me4R)2UBr2] (R = Me, Et)
Inorganics 2016, 4(1), 1; doi:10.3390/inorganics4010001
Received: 23 November 2015 / Revised: 9 December 2015 / Accepted: 11 December 2015 / Published: 6 January 2016
Cited by 1 | PDF Full-text (2914 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The organometallic uranium species (C5Me4R)2UBr2 (R = Me, Et) were obtained by treating their chloride analogues (C5Me4R)2UCl2 (R = Me, Et) with Me3SiBr. Treatment of (C5
[...] Read more.
The organometallic uranium species (C5Me4R)2UBr2 (R = Me, Et) were obtained by treating their chloride analogues (C5Me4R)2UCl2 (R = Me, Et) with Me3SiBr. Treatment of (C5Me4R)2UCl2 and (C5Me4R)2UBr2 (R = Me, Et) with K(O-2,6-iPr2C6H3) afforded the halide aryloxide mixed-ligand complexes (C5Me4R)2U(O-2,6-iPr2C6H3)(X) (R = Me, Et; X = Cl, Br). Complexes (C5Me4R)2U(O-2,6-iPr2C6H3)(Br) (R = Me, Et) can also be synthesized by treating (C5Me4R)2U(O-2,6-iPr2C6H3)(Cl) (R = Me, Et) with Me3SiBr, respectively. Reduction of (C5Me4R)2UCl2 and (C5Me4R)2UBr2 (R = Me, Et) with KC8 led to isolation of uranium(III) “ate” species [K(THF)][(C5Me5)2UX2] (X = Cl, Br) and [K(THF)0.5][(C5Me4Et)2UX2] (X = Cl, Br), which can be converted to the neutral complexes (C5Me4R)2U[N(SiMe3)2] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented. Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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Open AccessCommunication Synthesis and Characterization of Cerium(IV) Metallocenes
Inorganics 2015, 3(4), 589-596; doi:10.3390/inorganics3040589
Received: 24 October 2015 / Revised: 1 December 2015 / Accepted: 4 December 2015 / Published: 11 December 2015
Cited by 6 | PDF Full-text (777 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
By applying a salt metathesis approach between Ce(OtBu3)2(NO3)2(THF)2 and the potassium salts of mono- and ditrimethylsilyl substituted cyclopentadienes, we were able to isolate two new Ce(IV) metallocenes, including to the best of our knowledge, the first structurally characterized bis-cyclopentadiene Ce(IV) compound. Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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Open AccessArticle On the Dehydrocoupling of Alkenylacetylenes Mediated by Various Samarocene Complexes: A Charming Story of Metal Cooperativity Revealing a Novel Dual Metal σ-Bond Metathesis Type of Mechanism (DM|σ-BM)
Inorganics 2015, 3(4), 573-588; doi:10.3390/inorganics3040573
Received: 30 September 2015 / Revised: 24 November 2015 / Accepted: 26 November 2015 / Published: 4 December 2015
Cited by 1 | PDF Full-text (1135 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The prevailing reductive chemistry of Sm(II) has been accessed and explored mostly by the use of samarocene precursors. The highly reducing character of these congeners, along with their Lewis acidity and predominantly ionic bonding, allows for the relatively facile activation of C–H bonds,
[...] Read more.
The prevailing reductive chemistry of Sm(II) has been accessed and explored mostly by the use of samarocene precursors. The highly reducing character of these congeners, along with their Lewis acidity and predominantly ionic bonding, allows for the relatively facile activation of C–H bonds, as well as peculiar transformations of unsaturated substrates (e.g., C–C couplings). Among other important C–C coupling reactions, the reaction of phenylacetylene with different mono- or bimetallic samarocene complexes affords trienediyl complexes of the type {[(C5Me5)2Sm]2(µ-η22-PhC4Ph)}. In contrast, when t-butylacetylene is used, uncoupled monomers of the type (C5Me5)2Sm(C≡C–tBu) were obtained. Although this type of reactivity may appear to be simple, the mechanism underlying these transformations is complex. This conclusion is drawn from the density functional theory (DFT) mechanistic studies presented herein. The operating mechanistic paths consist of: (i) the oxidation of each samarium center and the concomitant double reduction of the alkyne to afford a binuclear intermediate; (ii) the C–H scission of the acetylinic bond that lies in between the two metals; (iii) a dual metal σ-bond metathesis (DM|σ-SBM) process that releases H2; and eventually (iv) the C–C coupling of the two bridged μ-alkynides to give the final bimetallic trienediyl complexes. For the latter mechanistic route, the experimentally used phenylacetylene was considered first as well as the aliphatic hex-1-yne. More interestingly, we shed light into the formation of the mono(alkynide) complex, being the final experimental product of the reaction with t-butylacetylene. Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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Open AccessArticle Magnetic and Photo-Physical Properties of Lanthanide Dinuclear Complexes Involving the 4,5-Bis(2-Pyridyl-N-Oxidemethylthio)-4′,5′-Dicarboxylic Acid-Tetrathiafulvalene-, Dimethyl Ester Ligand
Inorganics 2015, 3(4), 554-572; doi:10.3390/inorganics3040554
Received: 15 October 2015 / Revised: 13 November 2015 / Accepted: 23 November 2015 / Published: 3 December 2015
Cited by 1 | PDF Full-text (3086 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The reaction between the 4,5-bis(2-pyridyl-N-oxidemethylthio)-4′,5′-dicarboxylic acid-tetrathiafulvalene-, dimethyl ester ligand (L) and the metallo-precursors Ln(hfac)3·2H2O leads to the formation of two dinuclear complexes of formula [Ln2(hfac)6(L)]·(CH2Cl2)·(C
[...] Read more.
The reaction between the 4,5-bis(2-pyridyl-N-oxidemethylthio)-4′,5′-dicarboxylic acid-tetrathiafulvalene-, dimethyl ester ligand (L) and the metallo-precursors Ln(hfac)3·2H2O leads to the formation of two dinuclear complexes of formula [Ln2(hfac)6(L)]·(CH2Cl2)·(C6H14)0.5 (LnIII = DyIII (1) and YbIII (2)). The X-ray structure reveals a quite regular square anti-prism symmetry for the coordination sphere of the lanthanide ion. UV-visible absorption properties have been experimentally measured and rationalized by TD-DFT calculations. The functionalization of the tetrathiafulvalene (TTF) core by two methyl ester moieties induces the appearance of an additional absorption band in the lowest-energy region of the spectrum. The latter has been identified as a HOMO (Highest Occupied Molecular Orbital)→LUMO (Lowest Unoccupied Molecular Orbital) Intra-Ligand Charge Transfer (ILCT) transition in which the HOMO and LUMO are centred on the TTF and methyl ester groups, respectively. Irradiation at 22,222 cm−1 of this ILCT band induces an efficient sensitization of the YbIII-centred emission that can be correlated to the magnetic properties. Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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Open AccessArticle Synthesis and Reactivity of a Cerium(III) Scorpionate Complex Containing a Redox Non-Innocent 2,2′-Bipyridine Ligand
Inorganics 2015, 3(4), 534-553; doi:10.3390/inorganics3040534
Received: 14 September 2015 / Revised: 30 October 2015 / Accepted: 17 November 2015 / Published: 27 November 2015
Cited by 2 | PDF Full-text (1741 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The Ce(III) hydrotris(3,5-dimethylpyrazolyl)borate complex [Ce(TpMe2)22-dmpz)] (1) (TpMe2 = {HB(dmpz)3}; dmpz = 3,5-dimethylpyrazolide) was isolated in fair yield from the reaction of [Ce(I)3(THF)4] with two equivalents of
[...] Read more.
The Ce(III) hydrotris(3,5-dimethylpyrazolyl)borate complex [Ce(TpMe2)22-dmpz)] (1) (TpMe2 = {HB(dmpz)3}; dmpz = 3,5-dimethylpyrazolide) was isolated in fair yield from the reaction of [Ce(I)3(THF)4] with two equivalents of [K(TpMe2)] via the facile decomposition of TpMe2. [Ce(TpMe2)2(bipy)] (2) was synthesized in poor yield by the “one-pot” reaction of [Ce(I)3(THF)4], bipy (bipy = 2,2′-bipyridine), KC8 and two equivalents of [K(TpMe2)] in tetrahydrofuran (THF). The reaction of 2 with N-methylmorpholine-N-oxide produced the known decomposition product [Ce(TpMe2)(μ-BOpMe2)]2 (3) (BOpMe2 = {HBO(dmpz)2}2−) in poor yield, presumably by N–O and B–N bond cleavage of a reactive intermediate. The reaction of 2 with trimethylsilylazide gave [Ce(TpMe2)2(N3)] (4) in poor yield; the fate of bipy and the trimethylsilyl group is unknown. Complexes 14 were characterized by single crystal XRD, NMR and FTIR spectroscopy and elemental analysis. Complex 2 was additionally probed by UV/Vis/NIR and Electron Paramagnetic Resonance (EPR) spectroscopies, Cyclic Voltammetry (CV) and magnetometry, which together indicate a formal 4f1 Ce(III) center coordinated by a bipy· radical anion in this system. Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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Open AccessArticle Gadolinium(III)-DOTA Complex Functionalized with BODIPY as a Potential Bimodal Contrast Agent for MRI and Optical Imaging
Inorganics 2015, 3(4), 516-533; doi:10.3390/inorganics3040516
Received: 29 September 2015 / Revised: 10 November 2015 / Accepted: 17 November 2015 / Published: 25 November 2015
Cited by 2 | PDF Full-text (1483 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The synthesis and characterization of a novel gadolinium(III) DOTA complex functionalized with a boron-dipyrromethene derivative (BODIPY) is described. The assembly of the complex relies on azide diazotransfer chemistry in a copper tube flow reactor. The azide thus formed is coupled directly with an
[...] Read more.
The synthesis and characterization of a novel gadolinium(III) DOTA complex functionalized with a boron-dipyrromethene derivative (BODIPY) is described. The assembly of the complex relies on azide diazotransfer chemistry in a copper tube flow reactor. The azide thus formed is coupled directly with an alkyne via click chemistry, resulting into a paramagnetic and luminescent gadolinium(III) complex. Luminescent data and relaxometric properties of the complex have been evaluated, suggesting the potential applicability of the complexes as a bimodal contrast agent for magnetic resonance and optical imaging. The complex displays a bright emission at 523 nm with an absorption maximum of 507 nm and high quantum yields of up to 83% in water. The proton relaxivity of the complex measured at 310 K and at frequencies of 20 and 60 MHz had the values of 3.9 and 3.6 s1·mM1, respectively. Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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Open AccessCommunication Holmium(III) Supermesityl-Imide Complexes Bearing Methylaluminato/Gallato Ligands
Inorganics 2015, 3(4), 500-510; doi:10.3390/inorganics3040500
Received: 22 September 2015 / Revised: 28 October 2015 / Accepted: 30 October 2015 / Published: 10 November 2015
Cited by 1 | PDF Full-text (911 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Heterobimetallic µ2-imide complexes [Ho(µ2-Nmes*){Al(CH3)4}]2 (1, supermesityl = mes* = C6H2tBu3-2,4,6) and [Ho(µ2-Nmes*){Ga(CH3)4}]2 (2) have been synthesized
[...] Read more.
Heterobimetallic µ2-imide complexes [Ho(µ2-Nmes*){Al(CH3)4}]2 (1, supermesityl = mes* = C6H2tBu3-2,4,6) and [Ho(µ2-Nmes*){Ga(CH3)4}]2 (2) have been synthesized from homoleptic complexes Ho[M(CH3)4]3 (M = Al, Ga) via deprotonation of H2Nmes* or with K[NH(mes*)] according to a salt metathesis-protonolysis tandem reaction. Single-crystal X-ray diffraction of isostructural complexes [Ho(µ2-Nmes*){M(CH3)4}]2 (M = Al, Ga) revealed asymmetric Ho2N2 metallacycles with very short Ho–N bond lengths and secondary Ho arene interactions. Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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Open AccessCommunication Luminescent Lanthanide Metal Organic Frameworks for cis-Selective Isoprene Polymerization Catalysis
Inorganics 2015, 3(4), 467-481; doi:10.3390/inorganics3040467
Received: 18 September 2015 / Revised: 27 October 2015 / Accepted: 29 October 2015 / Published: 9 November 2015
Cited by 2 | PDF Full-text (3389 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
In this study, we are combining two areas of chemistry; solid-state coordination polymers (or Metal-Organic Framework—MOF) and polymerization catalysis. MOF compounds combining two sets of different lanthanide elements (Nd3+, Eu3+/Tb3+) were used for that purpose: the use
[...] Read more.
In this study, we are combining two areas of chemistry; solid-state coordination polymers (or Metal-Organic Framework—MOF) and polymerization catalysis. MOF compounds combining two sets of different lanthanide elements (Nd3+, Eu3+/Tb3+) were used for that purpose: the use of neodymium was required due to its well-known catalytic properties in dienes polymerization. A second lanthanide, europium or terbium, was included in the MOF structure with the aim to provide luminescent properties. Several lanthanides-based MOF meeting these criteria were prepared according to different approaches, and they were further used as catalysts for the polymerization of isoprene. Stereoregular cis-polyisoprene was received, which in some cases exhibited luminescent properties in the UV-visible range. Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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Open AccessArticle Assessing Covalency in Cerium and Uranium Hexachlorides: A Correlated Wavefunction and Density Functional Theory Study
Inorganics 2015, 3(4), 482-499; doi:10.3390/inorganics3040482
Received: 14 September 2015 / Revised: 29 October 2015 / Accepted: 30 October 2015 / Published: 9 November 2015
Cited by 8 | PDF Full-text (1443 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The electronic structure of a series of uranium and cerium hexachlorides in a variety of oxidation states was evaluated at both the correlated wavefunction and density functional (DFT) levels of theory. Following recent experimental observations of covalency in tetravalent cerium hexachlorides, bonding character
[...] Read more.
The electronic structure of a series of uranium and cerium hexachlorides in a variety of oxidation states was evaluated at both the correlated wavefunction and density functional (DFT) levels of theory. Following recent experimental observations of covalency in tetravalent cerium hexachlorides, bonding character was studied using topological and integrated analysis based on the quantum theory of atoms in molecules (QTAIM). This analysis revealed that M–Cl covalency was strongly dependent on oxidation state, with greater covalency found in higher oxidation state complexes. Comparison of M–Cl delocalisation indices revealed a discrepancy between correlated wavefunction and DFT-derived values. Decomposition of these delocalisation indices demonstrated that the origin of this discrepancy lay in ungerade contributions associated with the f-manifold which we suggest is due to self-interaction error inherent to DFT-based methods. By all measures used in this study, extremely similar levels of covalency between complexes of U and Ce in the same oxidation state was found. Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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Open AccessArticle Dinuclear Lanthanide (III) Coordination Polymers in a Domino Reaction
Inorganics 2015, 3(4), 448-466; doi:10.3390/inorganics3040448
Received: 13 October 2015 / Revised: 26 October 2015 / Accepted: 29 October 2015 / Published: 6 November 2015
Cited by 3 | PDF Full-text (2111 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
A systematic study was performed to further optimise the catalytic room-temperature synthesis of trans-4,5-diaminocyclopent-2-enones from 2-furaldehyde and primary or secondary amines under a non-inert atmosphere. For this purpose, a series of dinuclear lanthanide (III) coordination polymers were synthesised using a dianionic Schiff
[...] Read more.
A systematic study was performed to further optimise the catalytic room-temperature synthesis of trans-4,5-diaminocyclopent-2-enones from 2-furaldehyde and primary or secondary amines under a non-inert atmosphere. For this purpose, a series of dinuclear lanthanide (III) coordination polymers were synthesised using a dianionic Schiff base and their catalytic activities were investigated. Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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Open AccessArticle New Lanthanide Alkynylamidinates and Diiminophosphinates
Inorganics 2015, 3(4), 429-447; doi:10.3390/inorganics3040429
Received: 7 October 2015 / Revised: 23 October 2015 / Accepted: 27 October 2015 / Published: 5 November 2015
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Abstract
This contribution reports the synthesis and structural characterization of several new lithium and lanthanide alkynylamidinate complexes. Treatment of PhC≡CLi with N,N′-diorganocarbodiimides, R–N=C=N–R (R = iPr, Cy (cyclohexyl)), in THF or diethyl ether solution afforded the lithium-propiolamidinates Li[Ph–C≡C–C(NCy)2]
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This contribution reports the synthesis and structural characterization of several new lithium and lanthanide alkynylamidinate complexes. Treatment of PhC≡CLi with N,N′-diorganocarbodiimides, R–N=C=N–R (R = iPr, Cy (cyclohexyl)), in THF or diethyl ether solution afforded the lithium-propiolamidinates Li[Ph–C≡C–C(NCy)2] S (1: R = iPr, S = THF; 2: R = Cy, S = THF; 3: R = Cy, S = Et2O). Single-crystal X-ray diffraction studies of 1 and 2 showed the presence of typical ladder-type dimeric structures in the solid state. Reactions of anhydrous LnCl3 (Ln = Ce, Nd, Sm or Ho) with 2 in a 1:3 molar ratio in THF afforded a series of new homoleptic lanthanide tris(propiolamidinate) complexes, [Ph–C≡C–C(NCy)2]3Ln (4: Ln = Ce; 5: Ln = Nd; 6: Ln = Sm; 7: Ln = Ho). The products were isolated in moderate to high yields (61%–89%) as brightly colored, crystalline solids. The chloro-functional neodymium(III) bis(cyclopropylethynylamidinate) complex [{c-C3H5–C≡C–C(NiPr)2}2Ln(µ-Cl)(THF)]2 (8) was prepared from NdCl3 and two equiv. of Li[c-C3H5–C≡C–C(NiPr)2] in THF and structurally characterized. A new monomeric Ce(III)-diiminophosphinate complex, [Ph2P(NSiMe3)2]2Ce(µ-Cl)2Li(THF)2 (9), has also been synthesized in a similar manner from CeCl3 and two equiv. of Li[Ph2P(NSiMe3)2]. Structurally, this complex resembles the well-known “ate” complexes (C5Me5)2Ln(µ-Cl)2Li(THF)2. Attempts to oxidize compound 9 using trityl chloride or phenyliodine(III) dichloride did not lead to an isolable cerium(IV) species. Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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Review

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Open AccessReview Molecular Pnictogen Activation by Rare Earth and Actinide Complexes
Inorganics 2015, 3(4), 597-635; doi:10.3390/inorganics3040597
Received: 1 October 2015 / Revised: 4 December 2015 / Accepted: 9 December 2015 / Published: 21 December 2015
Cited by 6 | PDF Full-text (2925 KB) | HTML Full-text | XML Full-text
Abstract
This review covers the activation of molecular pnictogens (group 15 elements) by homogeneous rare earth and actinide complexes. All examples of molecular pnictogen activation (dinitrogen, white phosphorus, yellow arsenic) by both rare earths and actinides, to date (2015), are discussed, focusing on synthetic
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This review covers the activation of molecular pnictogens (group 15 elements) by homogeneous rare earth and actinide complexes. All examples of molecular pnictogen activation (dinitrogen, white phosphorus, yellow arsenic) by both rare earths and actinides, to date (2015), are discussed, focusing on synthetic methodology and the structure and bonding of the resulting complexes. Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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Open AccessReview Catalytic Organic Transformations Mediated by Actinide Complexes
Inorganics 2015, 3(4), 392-428; doi:10.3390/inorganics3040392
Received: 16 September 2015 / Revised: 7 October 2015 / Accepted: 9 October 2015 / Published: 30 October 2015
Cited by 10 | PDF Full-text (1098 KB) | HTML Full-text | XML Full-text
Abstract
This review article presents the development of organoactinides and actinide coordination complexes as catalysts for homogeneous organic transformations. This chapter introduces the basic principles of actinide catalysis and deals with the historic development of actinide complexes in catalytic processes. The application of organoactinides
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This review article presents the development of organoactinides and actinide coordination complexes as catalysts for homogeneous organic transformations. This chapter introduces the basic principles of actinide catalysis and deals with the historic development of actinide complexes in catalytic processes. The application of organoactinides in homogeneous catalysis is exemplified in the hydroelementation reactions, such as the hydroamination, hydrosilylation, hydroalkoxylation and hydrothiolation of alkynes. Additionally, the use of actinide coordination complexes for the catalytic polymerization of α-olefins and the ring opening polymerization of cyclic esters is presented. The last part of this review article highlights novel catalytic transformations mediated by actinide compounds and gives an outlook to the further potential of this field. Full article
(This article belongs to the Special Issue Rare Earth and Actinide Complexes) Printed Edition available
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