The reaction of N-heterocyclic carbene (NHC) with dimeric dialkylgallium alkoxides, acting as nonselective or heteroselective catalysts in the polymerization rac-LA, leads to highly active and isoselective monomeric Me2Ga(NHC)OR catalysts, resulting for first time facile switch stereoselectivity.

OR or OOR? The oxygenation of ZntBu2 in the presence donor ligands demonstrates tendency zinc dialkyls to undergo oxidation only one ZnC bond under controlled conditions (see scheme). formation alkoxide peroxide species is influenced by type ligand employed, and these divergent pathways offer a glimpse into general mechanism dioxygen activation.

The prepared in situ methyl(chloro)aluminum complex (2) from Me2AlCl and the pendant arm tridentate Schiff base (H-SchNMe2) was used to generate methylaluminum cationic species [(SchNMe2)AlMe]+ further reaction with 1 equiv of AlCl3 or NaBPh4 as chloride abstracting reagents. exposure resulting an excess dry dioxygen at 0 degrees C afforded alkoxyaluminum species, [(SchNMe2)AlOMe]+ [(SchNMe2)AlOPh]+. alkoxylaluminum cations proved be a very efficient catalyst polymerization epsilon-caprolactone.

The structure of a series Me2GaOR(NHC) complexes with N-heterocyclic carbenes (1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes)) have been characterized using spectroscopic X-ray techniques discussed in view their reactivity the polymerization rac-lactide (rac-LA). Both studies density functional theory (DFT) calculations show significant influence NHC OR on investigated has indicated that Ga–CNHC bond (32.6–39.6 kcal...

Abstract A new family of fluorine-free solid-polymer electrolytes, for use in sodium-ion battery applications, is presented. Three novel sodium salts withdiffuse negative charges: pentacyanopropenide (NaPCPI), 2,3,4,5-tetracyanopirolate (NaTCP) and 2,4,5-tricyanoimidazolate (NaTIM) were designed andtested a poly(ethylene oxide) (PEO) matrix as polymer electrolytes anall-solid battery. Due to unique, non-covalent structural configurations anions, improved ionic conductivities observed. As an...

We have authenticated the molecular and crystal structure of ZntBu2 constructed unprecedented 2D fabric using tert-butylzinc molecules 1,2-bis(4-pyridyl)ethane as building blocks. The X-ray analysis revealed that inorganic−organic polymeric chains were weaving to form by concerted C−H···π interactions involving pyridine rings. Subtle factors governing self-assembly processes leading a are discussed.

This article describes synthesis and basic electrochemical structural properties of newly designed sodium salts for application in liquid nonaqueous electrolytes. There has been two imidazole fluorine derivative synthesized: 4,5-dicyano-2-(trifluoromethyl)imidazolate (NaTDI) 4,5-dicyano-2-(pentafluoroethyl)imidazolate (NaPDI). The structure the confirmed by means Raman spectroscopy, nuclear magnetic resonance (13C NMR 19F NMR), X-ray diffraction, thermogravimetry (TGA), differential scanning...

Abstract Cyclic Ru‐phenolates were synthesized, and these compounds used as olefin metathesis catalysts. Investigation of their catalytic activity pointed out that, after activation with chemical agents, catalysts promote ring‐closing (RCM), enyne cross‐metathesis (CM) reactions, including butenolysis, good results. Importantly, latent are soluble in neat dicyclopentadiene (DCPD) show applicability ring‐opening polymeriyation (ROMP) this monomer.

The crystal structure of arsenolite, the cubic polymorph molecular arsenic(III) oxide, has been determined by single-crystal X-ray diffraction up to 30 GPa. bulk is monotonically compressed with no detectable anomalies 60% initial volume at experimental As4O6 compression exceeds that obtained various theoretical models within density functional theory framework. molecules are deformed toward a more tetrahedral shape. A surprising property arsenolite immersed in helium revealed above 3 GPa;...

This paper reviews the battery electrolyte technologies involving Hückel-type salts as a major component. The concept was initially proposed by M. Armand in 1995 and then explored several research groups. In present review studies on optimization of composition starting from molecular modeling through enhancing yield salt synthesis to structural characterization electrochemical performance are described. Furthermore, use optimized electrolytes variety lithium-ion post-lithium batteries is...

Building on our previous studies, which have demonstrated that homochiral propagating species—(R*,R*)-[Me2Ga(µ-OCH(Me)CO2R)]2—were crucial for the heteroselectivity of [Me2Ga(µ-OCH(Me)CO2Me)]2 in ring-opening polymerization (ROP) racemic lactide (rac-LA), we investigated effect alkyl groups structure and catalytic properties dialkylgallium alkoxides ROP rac-LA. Therefore, isolated characterized rac-[R2Ga(µ-OCH(Me)CO2Me]2 (R = Et (1), iPr (2) rac-[R2Ga(µ-OCH(Me)C5H4N]2 (3), (4)) complexes, to...

Abstract The synthesis, structure and thermal properties of a one-dimensional coordination polymer based on calcium bis(dimethylphosphate) (CaDMP) are reported. rod-like particles CaDMP crystallized from water in monoclinic space group P 2 1 / c , contained Ca[O P(OCH 3 ) ] polymeric chains consisting the octahedrally coordinated Ca 2+ ions bridged by tridentate dimethylphosphate ligands. variable temperature powder X-ray diffraction measurements showed that this undergoes anisotropic...

The enantioselective resolution of several racemic derivatives mandelic acid methyl ester catalyzed by lipases from Pseudomonas fluorescens (Amano AK) or Burkholderia cepacia PS‐C II and Amano PS‐IM) has been achieved. A gram‐scale lipase‐mediated kinetic approach developed that allows the facile synthesis corresponding ( R )‐(–)‐mandelates with excellent enantiomeric excesses (up to >99 % ee ) reaction enantioselectivity E values up >200). dopaminergic agent pemoline, used in...

Chiral recognition of monomeric Me₂MOR units resulting in the formation homochiral dimeric species [Me₂M(μ-OR)]₂(M = Ga, In), leads to heteroselective catalysts for ring opening polymerization of<italic>rac</italic>-lactide (<italic>rac</italic>-LA).

The reaction of MMe3 with 1 molar equiv N-phenylsalicylideneimine (HsaldPh) yields the O,N-chelate complexes Me2M(saldPh) (where M = Al (1), Ga (2), In (3)) in high yields. γ-picoline results a ligand redistribution and formation five-coordinate complex MeAl(saldPh)2 (4), while gallium indium compounds are stable presence γ-picoline. resulting have been characterized solution by NMR IR spectroscopy cryoscopic molecular weight measurements, their crystal structure determined X-ray...

OR oder OOR? Am Beispiel der Oxygenierung von ZntBu2 in Gegenwart Donorliganden zeigt sich die Neigung Dialkylzink zur Oxidation nur einer Zn-C-Bindung unter bestimmten Bedingungen (siehe Schema). Ob dabei Alkoxid- Peroxid-Spezies entstehen, hängt vom eingesetzten ab. Diese divergenten Reaktionswege geben Einblick den allgemeinen Mechanismus Disauerstoff-Aktivierung.

Stereoselective polymerization of rac ‐lactide is one the most important issues as properties polylactide (PLA) depend strongly on its tacticity. There is, however, a paucity catalysts that allow for easy switching between heteroselectivity and isoselectivity, which limits synthesis stereo copolymers PLA modification properties. Dialkylgallium alkoxides activated by organosuperbases have been used in ring‐opening racemic lactide ( ‐LA). The reaction S , )‐[Me 2 Ga(μ‐OCH(Me)CO Me)] 1 ) with...

Methods for the synthesis of dialkylgalium compounds with alkoxide or aryloxide ligands possessing N-heterocyclic carbene functionalities have been established. As a result, series dialkylgallium complexes Me2Ga(O,C) (1, 3–5), and Me2Ga(O,C)·Me3Ga (2, 6) is described, where (O,C) represents an monoanionic chelate ligand functionality. All fully characterized using spectroscopic X-ray techniques. The presence strongly basic NHC functionality in resulted formation monomeric species. reaction...

We present complementary series of crystal structures lithium salts containing 4,5-dicyanoimidazolato anions substituted with perfluoroalkyl groups. Single-crystal X-ray analysis 10 adducts aprotic solvents, glymes (dimethyl ethers poly(ethylene glycols)) and crown ethers, have been performed to correlate their molecular properties spectroscopic thermal data. Comprehensive structure crystalline materials reveals valuable information about the coordination ability provides basis for...

Highly concentrated electrolytes based on Li-salts and chelating solvents, such as glymes, are promising for lithium batteries. This is due to their unique properties, higher electrochemical stabilities, compliance with high-voltage electrodes, low volatility flammability, inertness toward aluminum current collector corrosion. The nature of these properties originates from the molecular-level structure created in either solvate ionic liquids (SILs) or less common aggregates by...

In this paper we present the synthesis route and electrochemical properties of new class ionic liquids (ILs) obtained from lithium derivate TDI (4,5-dicyano-2-(trifluoromethyl)imidazolium) anion. ILs synthesized by us were EMImTDI, PMImTDI BMImTDI, i.e. anion with 1-alkyl-3-methylimidazolium cations, where alkyl meant ethyl, propyl butyl groups. contains fewer fluorine atoms than LiPF6 thanks to C-F instead P-F bond, they are less prone emit or hydrogen fluoride due rise in temperature. Use...

Abstract We hereby present the new class of ionic liquid systems in which lithium salt is introduced into solution as a cation−glyme solvate. This modification leads to reorganisation structure, entails release free mobile cation solvate and hence significant enhancement conductivity transference numbers. approach composing electrolytes also enables even three-fold increase concentration liquids.