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Inorganics, Volume 3, Issue 4 (December 2015), Pages 388-635

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Editorial

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Open AccessEditorial Inorganic Syntheses Assisted by Microwave Heating
Inorganics 2015, 3(4), 388-391; doi:10.3390/inorganics3040388
Received: 28 August 2015 / Accepted: 13 October 2015 / Published: 16 October 2015
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Abstract
This Special Issue on “Inorganic Syntheses Assisted by Microwave Heating” represents one of the few fully dedicated issues on inorganic microwave synthesis published by any international scientific journal and it features five papers and one review article. [...] Full article
(This article belongs to the Special Issue Inorganic Syntheses Assisted by Microwave Heating)
Open AccessEditorial The Fascination of Polyoxometalate Chemistry
Inorganics 2015, 3(4), 511-515; doi:10.3390/inorganics3040511
Received: 10 November 2015 / Revised: 16 November 2015 / Accepted: 19 November 2015 / Published: 23 November 2015
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Abstract
We are delighted to introduce this special issue of Inorganics. [...] Full article
(This article belongs to the Special Issue Polyoxometalates) Printed Edition available

Research

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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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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
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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 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
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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
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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
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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 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
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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
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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 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
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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
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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 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
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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
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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 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
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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
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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 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
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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,
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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 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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Review

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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
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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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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
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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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