Search results for "Organic chemistry"

Carbon Monoxide Activation by a Molecular Aluminium Imide: C−O Bond Cleavage and C−C Bond Formation

2020

Anionic molecular imide complexes of aluminium are accessible via a rational synthetic approach involving the reactions of organo azides with a potassium aluminyl reagent. In the case of K 2 [( NON )Al(NDipp)] 2 ( NON = 4,5‐bis(2,6‐di iso propylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethyl‐xanthene; Dipp = 2,6‐di iso propylphenyl) structural characterization by X‐ray crystallography reveals a short Al‐N distance, which is thought to be due primarily to the low coordinate nature of the nitrogen centre. The Al‐N unit is highly polar, and capable of the activation of relatively inert chemical bonds, such as those found in dihydrogen and carbon monoxide. In the case of CO, uptake of two molecules of …

Addition of Ethylene or Hydrogen to a Main-Group Metal Cluster under Mild Conditions

2015

Reaction of the tin cluster Sn8(Arinline image)4 (Arinline image=C6H2-2,6-(C6H3-2,4,6-Me3)2) with excess ethylene or dihydrogen at 25 °C/1 atmosphere yielded two new clusters that incorporated ethylene or hydrogen. The reaction with ethylene yielded Sn4(Arinline image)4(C2H2)5 that contained five ethylene moieties bridging four aryl substituted tin atoms and one tin–tin bond. Reaction with H2 produced a cyclic tin species of formula (Sn(H)Arinline image)4, which could also be synthesized by the reaction of {(Arinline image)Sn(μ-Cl)}2 with DIBAL-H. These reactions represent the first instances of direct reactions of isolable main-group clusters with ethylene or hydrogen under mild conditions…

Trapping and Reactivity of a Molecular Aluminium Oxide Ion

2019

Aluminium oxides constitute an important class of inorganic compound that are widely exploited in the chemical industry as catalysts and catalyst supports. Due to the tendency for such systems to aggregate via Al‐O‐Al bridges, the synthesis of well‐defined, soluble, molecular models for these materials is challenging. Here we show that reactions of the potassium aluminyl complex K 2 [( NON )Al] 2 ( NON = 4,5‐bis(2,6‐diiso‐propylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene) with CO 2 , PhNCO and N 2 O all proceed via a common aluminium oxide intermediate. This highly reactive species can be trapped by coordination of a THF molecule as the anionic oxide complex [( NON )AlO(THF)] ‐ , which …

Low‐Valent Germanylidene Anions: Efficient Single‐Site Nucleophiles for Activation of Small Molecules

2021

Abstract Rare mononuclear and helical chain low‐valent germanylidene anions supported by cyclic (alkyl)(amino)carbene and hypermetallyl ligands were synthesised by stepwise reduction from corresponding germylene precursors via stable and isolable germanium radicals. The electronic structures of the anions can be described with ylidene and ylidone resonance forms with the Ge−C π‐electrons capable of binding even weak electrophiles. The germanylidene anions reacted with CO2 to give μ‐CO2‐κC:κO complexes, a rare coordination mode for low‐valent germanium and inaccessible for the related neutral germylones. These results implicate low‐valent germanylidene anions as efficient single‐site nucleop…

Adsorption of anionic dyes onto natural, thermally and chemically modified smectite clays

2014

Abstract The aim of this study was to determine the adsorption capacity of the smectite clays (from the overburden of the lignite deposit in Belchatow) for two anionic dyes, i.e. Reactive Blue 81 (RB-81) and Direct Blue 74 (DB-74). Additionally, the influence of the thermal and chemical (acid and alkali) clay modifications on the amount of bonded dyes was investigated. The adsorption capacity of the clay (natural and modified) was different for studied dyes and depended on the initial concentration and modification type. All the modified clays adsorbed the dyes at pH>pHPZC as the negatively charged surfaces of their particles (in accordance with the formula: AOH ↔ AO- + H+) prevented the…

Extraordinary Performance of Carbon‐Coated Anatase TiO 2 as Sodium‐Ion Anode

2015

The synthesis of in situ polymer‐functionalized anatase TiO2 particles using an anchoring block copolymer with hydroxamate as coordinating species is reported, which yields nanoparticles (≈11 nm) in multigram scale. Thermal annealing converts the polymer brushes into a uniform and homogeneous carbon coating as proven by high resolution transmission electron microscopy and Raman spectroscopy. The strong impact of particle size as well as carbon coating on the electrochemical performance of anatase TiO2 is demonstrated. Downsizing the particles leads to higher reversible uptake/release of sodium cations per formula unit TiO2 (e.g., 0.72 eq. Na+ (11 nm) vs only 0.56 eq. Na+ (40 nm)) while the …

Synthesis and Biological Evaluation of a Multiantigenic Tn/TF-Containing Glycopeptide Mimic of the Tumor-Related MUC1 Glycoprotein

2006

Combined Use of Structure Analysis, Studies of Molecular Association in Solution, and Molecular Modelling to Understand the Different Propensities of…

2021

The arrangement of hydroxyl groups in the benzene ring has a significant effect on the propensity of dihydroxybenzoic acids (diOHBAs) to form different solid phases when crystallized from solution. All six diOHBAs were categorized into distinctive groups according to the solid phases obtained when crystallized from selected solvents. A combined study using crystal structure and molecule electrostatic potential surface analysis, as well as an exploration of molecular association in solution using spectroscopic methods and molecular dynamics simulations were used to determine the possible mechanism of how the location of the phenolic hydroxyl groups affect the diversity of solid phases formed…

Chasing Weak Forces: Hierarchically Assembled Helicates as a Probe for the Evaluation of the Energetics of Weak Interactions.

2017

London dispersion forces are the weakest interactions between molecules. Because of this, their influence on chemical processes is often low, but can definitely not be ignored, and even becomes important in cases of molecules with large contact surfaces. Hierarchically assembled dinuclear titanium(IV) helicates represent a rare example in which the direct observation of London dispersion forces is possible in solution even in the presence of strong cohesive solvent effects. Hereby, the dispersion forces do not unlimitedly support the formation of the dimeric complexes. Although they have some favorable enthalpic contribution to the dimerization of the monomeric complex units, large flexible…

Evaluation of the Behavior of Phenolic Compounds and Steviol Glycosides of Sonicated Strawberry Juice Sweetened with Stevia (Stevia rebaudiana Berton…

2019

In this study, the influence of stevia addition and sonication processing parameters on the phenolic content and profile as well as the steviol glycosides of strawberry juice-based samples was investigated. For this purpose, three matrices&mdash