Lateral thinking: A diagonal approach to CO2 recycling has been explored for the formation of both functionalized and energetic chemicals featuring a reduced carbon center. The strategy relies on tandem use functionalization reagent reductant that can be independently modified access wide spectrum from CO2. It is exemplified with an organocatalytic process convert into formamides (see picture). Detailed facts importance specialist readers are published as "Supporting Information". Such...

A novel calix[4]arene-based chemosensor 1 based on Hg2+-induced fluorescence resonance energy transfer (FRET) was synthesized, and its sensing behavior toward metal ions investigated by UV/vis spectroscopies. Addition of Hg2+ to a CH3CN solution gave significantly enhanced at ∼575 nm via (FRET-ON) from the pyrenyl excimer ring-opened rhodamine moiety. In contrast, addition Al3+ induced distinct increase emission (∼475 nm), while no obvious FRET-ON phenomenon observed. Different binding...

Treatment of U(BH(4))(4) with 1 or 3 equiv Li(2)(SCS) x 1.5 Et(2)O, 1, afforded the actinide carbene complexes U(mu-SCS)(3)[U(BH(4))(3)](2) (4) and U(mu-SCS)(3)[Li(Et(2)O)](2) (6), respectively [SCS = (Ph(2)P S)(2)C]. In THF, complex 4 was transformed into mononuclear derivative (SCS)U(BH(4))(2)(THF)(2) (5). The multiple bond character uranium-carbon first revealed by X-ray crystal structures three complexes. U=C in these present a nucleophilic character, as shown their reaction carbonyl...

Convergent reductive depolymerization of wood lignin to isolated phenol derivatives by metal-free catalytic hydrosilylation.

Guanidines and amidines prove to be highly efficient metal-free catalysts for the reduction of CO2 methanol with hydroboranes such as 9-borabicyclo[3.3.1]nonane (9-BBN) catecholborane (catBH). Nitrogen bases, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (Me-TBD), 1,8-diazabicycloundec-7-ene (DBU), are active this transformation Me-TBD can catalyze methoxyborane at room temperature TONs TOFs up 648 33 h(-1) (25 °C), respectively. Formate HCOOBR2...

Quergedacht: Mit einem diagonalen Ansatz zur Wiederverwertung von CO2 können funktionalisierte Chemikalien erhalten werden. Der Einsatz eines funktionalisierenden Reagens sowie Reduktionsmittels, die beide unabhängig voneinander modifiziert werden können, liefert ausgehend eine Vielzahl Chemikalien. Die organokatalytische Umsetzung zu Formamid (siehe Bild) dient als ein Beispiel.

Uranyl organometallic complexes featuring uranium(VI)-carbon single and double bonds have been obtained from uranyl UO(2)X(2) precursors by avoiding reduction of the metal center. X-ray diffraction density functional theory analyses these showed that U-C U=C are polarized toward nucleophilic carbon.

Abstract Molecular designs merging circularly polarized luminescence (CPL) and thermally activated delayed fluorescence (CP‐TADF) using the concept of chiral perturbation appeared recently as a cornerstone for development efficient CP‐organic light emitting diodes (CP‐OLED). Such devices could strongly increase energy efficiency performances conventional OLED displays, in which 50% emitted is often lost due to use antiglare filters. In this context, herein, ten couples enantiomers derived...

A series of nine complexes has been obtained from the hydrothermal reaction uranyl nitrate with long-chain alkyldicarboxylic acids (HOOC-(CH2)n–2-COOH, denoted H2Cn) in presence cucurbit[6]uril (CB6), dimethylformamide (DMF), which generates dimethylammonium cations situ, and additional alkaline-earth metal ions some cases. The crystal structures three [H2NMe2]2[(UO2)4O2(OH)2(C8)2(CB6)]·8H2O (1), [H2NMe2]2[(UO2)4O2(OH)2(C9)2(CB6)]·5H2O (2), [H2NMe2]2[(UO2)4O2(OH)2(C9)2(CB6)]·8H2O (3) are...

A series of base-stabilized silylium species were synthesized and their reactivity toward CO2 explored, yielding the characterization a novel N/Si+ FLP-CO2 adduct. These silicon are active catalysts in hydroboration to methoxide level with 9-BBN, catecholborane (catBH), pinacolborane (pinBH). Both experiments DFT calculations highlight role adduct catalysis. Depending on nature hydroborane reductant, two distinct mechanisms have been unveiled. While 9-BBN catBH able reduce an intermediate...

The four-electron reduction of CO2 in the presence secondary aromatic amines is described for first time to access aminals. Under metal-free hydrosilylation conditions, four C–O bonds are cleaved, and organocatalysts able balance reactivity promote selective formation two C–N C–H bonds. methodology enables various symmetrical unsymmetrical

An overview is given of recent structural studies on heterometallic uranyl-containing species, with particular emphasis those formed carboxylate ligands, showing the effect additional metal cations and ancillary ligands dimensionality, geometry topology assemblies generated. These examples illustrate level elaboration which now possible in design synthesis both uranyl clusters coordination polymers, properties potential applications are also briefly discussed.

Structural studies of uranyl ion complexes metalloligands and zwitterions, ligand classes with some degree overlap, constitute a major contribution to more recent developments in uranium chemistry. To extent, they have been focussed on basic product characterization but generally gaining an understanding how particular features structure may influence the complete crystal thus potential for any applications. Metalloligands provide obvious means generating heterometallic since it is not...

Uranyl ion complexation by cucurbit[n]urils (CBn, n = 6, 7, 8) was investigated, mostly under hydrothermal conditions, and the crystal structure of six novel complexes determined. In compounds [UO2(H2O)5](NO3)2·CB6·4H2O (1) [UO2(NO3)2(H2O)2]·CB6·7H2O (2), CB6 acts as a second-sphere ligand through hydrogen bonding to uranyl aquo ligands, while in all other complexes, [(UO2)4(CB6)O2(OH)2(H2O)6](NO3)2·CB6·8H2O (3), [(UO2)2(CB6)3(H2O)6][(UO2)2(NO3)4(C10H16O4)]2·CB6·8H2O (4),...

We report a systematic study of structural and transport properties in single crystals $\text{Ba}{({\text{Fe}}_{1\ensuremath{-}x}{\text{Ru}}_{x})}_{2}{\text{As}}_{2}$ for $x$ ranging from 0 to 0.5. The isovalent substitution Fe by Ru leads an increase the $a$ parameter decrease $c$ parameter, resulting strong As-Fe-As angle As height above planes. On substitution, magnetic order is progressively suppressed superconductivity emerges $x\ensuremath{\ge}0.15$ with optimal...

Ein blühender Baum zeigt bildlich, wie CO2 mit einer Strategie, die T. Cantat et al. in ihrer Zuschrift auf S. 191 ff. vorstellen, zahlreichen Chemikalien wiederverwertet werden kann. Der Ansatz beruht der Kombination eines funktionalisierenden Reagens und Reduktionsmittels, unabhängig voneinander modifiziert können, um aus eine Vielzahl molekularer Produkte zu erhalten. Über direkte Umwandlung von CO2, Aminen Silanen Formamiden wird berichtet.

The reaction of [UO(2)I(2)(THF)3] with KC(5)R(5) (R = H, Me) or K(2)C(8)H(8) in pyridine gave crystals [{UO(2)(py)(5)}{KI2(py)2}]. (1), which were desolvated under vacuum into pulverulent [UO(2)(py)2.2KI2] (2).Similar reactions [UO2(OTf)2] afforded [UO2(py)2.3K(OTf)2] (3) as a powder and [{UO(2)(py)(5)}2{K(3)(OTf)(5)}. py]. (4.py), also obtained together [{UO2(py)5}2{K(OTf)2(py)2}][OTf] py (5. py) by treating KC(4)Me(4)P. Crystals 6. py, the thallium analogue 5. isolated from TlC5H5....

Abstract The disproportionation of formic acid to methanol was unveiled in 2013 using iridium catalysts. Although attractive, this transformation suffers from very low yields; produced less than 2 % yield, because the competitive dehydrogenation (to CO and H ) is favored. We report herein efficient selective conversion HCOOH 50 utilizing ruthenium(II) phosphine complexes under mild conditions. Experimental theoretical (DFT) results show that different convergent pathways are involved...

The mono-, bis-, and tris-carbene uranium complexes [Li(THF)2U(SCS)Cl3(THF)] (2a), [U(SCS)2(THF)2] (3a), [{Li(OEt2)}2U(SCS)3] (1) were synthesized in good yields by reactions of UCl4 the stoichiometric amount Li2(SCS) [(SCS)2– = [Ph2P(═S)]2C2–]. Complex 3a was also obtained comproportionation reaction 1 0.5 molar equiv further reacted with to give neutral mono-carbene [U(SCS)Cl2(THF)2] (5a). Treatment U(NEt2)4 H2C(Ph2PS)2 THF led a mixture [U(SCS)(NEt2)2] (6), while same Et2O gave mixed...

Uranyl nitrate was reacted with several polycarboxylic acids under solvo-/hydrothermal conditions using N-methyl-2-pyrrolidone (NMP) as the organic component to give six novel complexes, which were crystallographically characterized. NMP is coordinated uranyl ion in all cases but one. The complex terephthalic acid (H2tph), [UO2(tph)(NMP)] (1), crystallizes a three-dimensional (3D) framework, an unprecedented feature complexes this ligand. two obtained 2,5-thiophenedicarboxylic (H2thd),...

4,4'-Biphenyldicarboxylic acid (H2L) was reacted with uranyl ions under solvo-hydrothermal conditions variations in the experimental procedure (organic cosolvent, presence of additional 3d-block metal cations, and N-donor species), thus giving six complexes fully deprotonated that were characterized by their crystal structure and, most cases, emission spectrum. The three [UO2(L)(DMA)] (1), [UO2(L)(NMP)] (2), (3) include cosolvent as a coligand, they crystallize two-dimensional (2D)...

The reaction of 1,3-adamantanedicarboxylic acid (LH2) with uranyl nitrate under solvo-hydrothermal conditions, either alone or in the presence additional metal cations (Co2+, Ni2+, Cu2+) gives a series nine complexes displaying wide range architectures. While [UO2(L)(H2O)]·1.25CH3CN (1) and [UO2(L)(DMF)] (2) are one-dimensional (1D) species analogous to that previously known, [H2NMe2]2[(UO2)2(L)3]·1.5H2O (3), which includes dimethylammonium counterions generated situ, is three-dimensional...

trans-1,4-Cyclohexanedicarboxylic acid (t-1,4-chdcH2) or the commercially available mixture of cis and trans isomers (c,t-1,4-chdcH2) has been used in synthesis a series 14 uranyl ion complexes, all obtained under solvohydrothermal conditions, some presence additional metal cations and/or 2,2′-bipyridine (bipy). With its two isomeric forms having very different shapes great sensitivity to experimental 1,4-chdc2– appears be suitable for complexes displaying wide range architectures. Under...