Search results for "11"
showing 10 items of 17291 documents
Iminium Catalysis (n → π*)
2016
Oxidovanadium(V) amine bisphenolates as epoxidation, sulfoxidation and catechol oxidation catalysts
2017
Air-stable oxidovanadium(V) complexes with tetradentate amine bisphenolate ligands were made by the reaction of VOSO4·xH2O and ligand precursors in MeOH solutions. Isolated compounds were studied as catechol oxidase models as well as catalysts for epoxidation and sulfoxidation reactions. All compounds can catalyse such oxidation reactions without notable structure-activity correlations. The 51V NMR studies indicate that the complexes turn to the number of different species during the catalytic experiments. peerReviewed
Enantioselective synthesis of 4H-pyranonaphthoquinones via sequential squaramide and silver catalysis
2015
Chemical communications 52(8), 1669-1672(2016). doi:10.1039/C5CC09592A
Gold/Isophorone Interaction Driven by Keto/Enol Tautomerization
2016
The binding behavior of isophorone (C9H14O) to Au adatoms and clusters deposited on MgO/Ag(001) thin films is investigated by scanning tunneling microscopy (STM) and density functional theory (DFT). The STM data reveal the formation of various metal/organic complexes, ranging from Au1/isophorone pairs to larger Au aggregates with molecules bound to their perimeter. DFT calculations find the energetically preferred keto-isophorone to be unreactive toward gold, while the enol-tautomer readily binds to Au monomers and clusters. The interaction is governed by electrostatic forces between the hydroxyl group of the enol and negative excess charges residing on the ad-gold. The activation barrier b…
9,10-Phenanthrenedione as Visible-Light Photoredox Catalyst: A Green Methodology for the Functionalization of 3,4-Dihydro-1,4-Benzoxazin-2- Ones thro…
2018
A visible-light photoredox functionalization of 3,4-dihydro-1,4-benzoxazin-2-ones through a Friedel-Crafts reaction with indoles using an inexpensive organophotoredox catalyst is described. The reaction uses a dual catalytic system that is formed by a photocatalyst simple and cheap, 9,10-phenanthrenedione, and a Lewis acid, Zn(OTf)2. 5W white LEDs are used as visible-light source and oxygen from air as a terminal oxidant, obtaining the corresponding products with good yields. The reaction can be extended to other electron-rich arenes. Our methodology represents one of the most valuable and sustainable approach for the functionalization of 3,4-dihydro-1,4-benzoxazin-2-ones, as compared to th…
A novel MALDI-MS approach for the analysis of neutral metallosupramolecular architectures
2011
Matrix assisted laser desorption/ionisation mass spectrometry (MALDI-MS) methods have been developed for the characterisation of neutral [2×2] metallogrids derived fromdiimine, dihydrazone and diacylhydrazone ligands. Such grids may be protonated in solution to give cationic species but in most cases these are labile, so that rather delicate conditions are required for observation of the intact metallogrids as monoprotonated derivatives in the gas phase. As a MALDI matrix, 2,4,6-trihydroxyacetophenone (THAP) is sufficiently acidic to enable monoprotonation of the grids unaccompanied by dissociation, and if the grid sample is initially deposited by a layering technique to avoid any prelimina…
An aryl-fused redox-active tetrathiafulvalene with enhanced mixed-valence and radical-cation dimer stabilities.
2018
Molecular recognition of stable organic radicals is a relatively novel, but important structural binding motif in supramolecular chemistry. Here, we report on a redox-switchable veratrole-fused tetrathiafulvalene derivative VTTF which is ideally suited for this purpose and for the incorporation into stimuli-responsive systems. As revealed by electrochemistry, UV/Vis measurements, X-ray analysis, and electrocrystallisation, VTTF can be reversibly oxidised to the corresponding radical-cation or dication which shows optoelectronic and structural propterties similar to tetrathiafulvalene and tetrakis(methylthio)tetrathiafulvalene. However, theoretical calculations, variable temperature EPR, and…
Identification and H(D)-bond energies of C-H(D)Cl interactions in chloride-haloalkane clusters: a combined X-ray crystallographic, spectroscopic, and…
2016
The cationic (1,3,5-triazapentadiene)Pt(II) complex [Pt{NH[double bond, length as m-dash]C(N(CH2)5)N(Ph)C(NH2)[double bond, length as m-dash]NPh}2]Cl2 ([]Cl2) was crystallized from four haloalkane solvents giving [][Cl2(CDCl3)4], [][Cl2(CHBr3)4], [][Cl2(CH2Cl2)2], and [][Cl2(C2H4Cl2)2] solvates that were studied by X-ray diffraction. In the crystal structures of [][Cl2(CDCl3)4] and [][Cl2(CHBr3)4], the Cl(-) ion interacts with two haloform molecules via C-DCl(-) and C-HCl(-) contacts, thus forming the negatively charged isostructural clusters [Cl(CDCl3)2](-) and [Cl(CHBr3)2](-). In the structures of [][Cl2(CH2Cl2)2] and [][Cl2(C2H4Cl2)2], cations [](2+) are linked to a 3D-network by a syste…
Structural Tuning and Conformational Stability of Aromatic Oligoamide Foldamers
2017
A series of aromatic oligoamide foldamers with two or three pyridine-2,6-dicarboxamide units as their main folding motifs and varying aromatic building blocks as linkers have been synthetized to study the effects of the structural variation on the folding properties and conformational stability. Crystallographic studies showed that in the solid state the central linker unit either elongates the helices and more open S-shaped conformations, compresses the helices to more compact conformations or acts as a rigid spacer separating the pyridine-2,6-dicarboxamide units, which for their part add the predictability of the conformational properties. Multidimensional NMR studies showed that, even in…
A new hydrogen bonding motif involved in self-recognition in the solid state by functionalised macrocycles
2011
Self-recognition within the crystal lattices of three functionalised macrocycles results in the formation of arrays of remarkably similar hermaphroditic pairs of macrocycles. In the case of two of the macrocycles containing acylhydrazine substituents, a hitherto unknown recognition pattern is found in the interaction of the hydrazine moiety with crown-ether oxygen atoms.