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A Stable N-Heterocyclic Silylene with a 1,1′-Ferrocenediyl Backbone
(2020-10-15)
The N-heterocyclic silylene [{Fe(η⁵-C₅H4-NDipp)₂}Si] (1DippSi, Dipp=2,6-diisopropylphenyl) shows an excellent combination of pronounced thermal stability and high reactivity towards small molecules. It reacts readily with CO₂ and N₂O, respectively affording (1DippSiO₂)₂C and (1DippSiO)₂ as follow-up products of the silanone 1DippSiO. Its reactions with H₂O, NH₃, and FcPH₂ (Fc=ferrocenyl) furnish the respective oxidative addition products 1DippSi(H)X (X=OH, NH₂, PHFc). Its reaction with H₃BNH₃ unexpectedly results in ...
Aufsatz
Oxidation Reactions of the N-Heterocyclic Stannylenes [𝘰-C₆H₄ (NSi𝑡BuMe₂)]₂Sn and [{Fe(η⁵ -C₅H₄ -NSi𝑡BuMe₂)₂}Sn] with Sulfur, Selenium, and Diphenyl Diselenide
(2020-01-27)
The N‐heterocyclic stannylenes [{Fe(η$^5$‐C$_5$H$_4$‐NSi𝑡 BuMe$_2$)$_2$}Sn] (1 ) and [𝘰‐C$_6$H$_4$(NSi𝑡 BuMe$_2$)]$_2$Sn (2 ) were prepared in one‐pot reactions from SnCl$_2$, LiN(SiMe$_3$)$_2$, and the corresponding diamine, viz. [Fe(η$^5$‐C$_5$H$_4$‐NHSi𝑡 BuMe$_2$)$_2$] and 𝘰‐C$_6$H$_4$(NSiH𝘵 BuMe$_2$)$_2$, respectively. Oxidative addition reactions of 1 and 2 with S$_8$ and Se$_8$, respectively, afforded the corresponding 1,3,2,4‐dithiadistannetanes ((1 S$_2$), (2 S$_2$)), and 1,3,2,4‐diselenadistannetanes ...
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On the Influence of Microstructure on the Corrosion Behavior of Fe–Mn–Al–Ni Shape Memory Alloy in 5.0 wt% NaCl Solution
(2020-10-03)
Herein the corrosion behavior of Fe–Mn–Al–Ni shape memory alloys characterized by different microstructures in a 5.0 wt% NaCl solution is investigated. Open circuit potential and potentiodynamic polarisation tests are conducted. Generally, Fe–Mn–Al–Ni shows corrosion properties being similar to pure iron. However, the polarization curves of single crystals indicate the presence of an unstable passive system. The corrosion damage is analyzed by means of optical microscopy and electron microscopy. It is revealed that ...
Aufsatz
Combined leaching and plant uptake simulations of PFOA and PFOS under field conditions
(2020-08-31)
Per- and polyfluoroalkyl substances (PFASs) are used in industrial production and manufacturing but were repeatedly detected in agricultural soils and therefore in cash crops in recent years. Dissipation of perfluoroalkyl acids (PFAAs), a sub-group of PFASs, in the environment was rather attributed to the formation of non-extractable residues (NER) than to degradation or transformation. Currently, there are no models describing the fate of PFAAs in the soil-plant continuum under field conditions, which hampers an ...
Aufsatz
Bis‐[3]Ferrocenophanes with Central >E−E’< Bonds (E, E’=P, SiH): Preparation, Properties, and Thermal Activation
(2019-06-26)
A series of bis‐[3]ferrocenophanes of the general type Fe(C5H4E’)2E−E(E'C5H4)2Fe (E=P, SiH and E’=PtBu, NneoPentyl, NSi(CH3)3) with an isolobal molecular framework have been prepared and characterized by heteronuclear NMR spectroscopy and X‐ray crystallography. The thermal dissociation behavior with respect to homolytic fission of the central bond generating phosphorus centered radicals was investigated using EPR spectroscopy and quantum chemical calculations.
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Metallated [3]Ferrocenophanes Containing P3M Bridges (M = Li, Na, K)
(2018-07-11)
Alkali-metal phosphanides can be embedded into a [3]ferrocenophane scaffold giving rise to bicyclic ferrocenophanes [MFe(C5H4PtBu)2P] (M = Li, Na, K). Coordination of the alkali-metal ions takes place via the terminal phosphorus atoms adopting a puckered P3M four-membered ring. All compounds were characterized via single-crystal X-ray diffraction and multinuclear NMR spectroscopy (1H, 31P, 7Li), whereas 13C NMR data could only be recorded for the Li derivative, owing to the limited solubility of its heavier congeners ...
Aufsatz
Synthesis and crystal structure of μ-[1,1′-di(mesitylphosphanido)ferrocene]bis[η5-cyclopentadienylnickel(II)] tetrahydrofurane solvate, C42H48FeNi2OP2
(2018-03-08)
C42H48FeNi2OP2, orthorhombic, Pbca (no. 61), a = 9.4551(4) Å, b = 19.7133(9) Å, c = 39.693(2) Å, V = 7398.4(6) Å3, Z = 8, Rgt(F) = 0.0598, wRref(F2) = 0.1481, T = 100(2) K.
Aufsatz
S-Adenosyl-L-Homocysteine Hydrolase Inhibition by a Synthetic Nicotinamide Cofactor Biomimetic
(2018-03-21)
S-adenosyl-L-homocysteine (SAH) hydrolases (SAHases) are involved in the regulation of methylation reactions in many organisms and are thus crucial for numerous cellular functions. Consequently, their dysregulation is associated with severe health problems. The SAHase-catalyzed reaction is reversible and both directions depend on the redox activity of nicotinamide adenine dinucleotide (NAD+) as a cofactor. Therefore, nicotinamide cofactor biomimetics (NCB) are a promising tool to modulate SAHase activity. In the ...
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Cross-π-conjugated enediyne with multioptic metal binding sites
(2020-10-20)
The synthesis of an enediyne molecule functionlized with different metal coordination sites in a cross-pconjugated fashion is reported. Using Pd-mediated cross-coupling reactions, 2,20-bipyridine units were attached at the periphery of diazafluorenemethylidene to obtain a multitopic ligand. UV-vis spectrosopic investigations along with electrochemical analyses reveal electronic communication along the conjugated path reflected in red-shifted absorption spectra and shifts of reduction potentials. The properties of the ...
Aufsatz
N-tert-Alkyl-Substituted N-Heterocyclic Carbenes with a 1,1’-Ferrocenediyl Backbone
(2021-12-14)
1,1’-Diaminoferrocene (1) was converted to α-aminonitriles fc[NHC(CN)MeR’]₂ (fc=1,1’-ferrocenediyl; 2 a: R’=Me, 2 b: R’=Ph, 2 c: R’=tBu) by reaction with ketones MeC(O)R’ in the presence of NaCN/HOAc or to the diimine fc(N=CPh₂)₂ (3) by condensation with Ph₂CO. Treatment of 2 a–c or 3 with MeLi furnished fc(NHR)₂ (4 a: R=tBu, 4 b: R=CMe₂Ph, 4 c: R=CMe₂tBu, 4 d: R=CMePh₂) after aqueous work-up. The formylative cyclisation of 4 a–d to fc[(NR)₂CH][BF₄] (5H[BF₄]) was possible only for R=CMe₃ (a) and CMe₂Ph (b). The ...