1,721,083 research outputs found
Crystallographic study of manganese(III)acetylacetonate: An advanced undergraduate project with unexpected challenges
No full textSolvent-dependent moulding of porphyrin-based nanostructures: solid state, solution and on surface self-assembly
Full text linkA novel porphyrin derivative 1∙Zn was synthesised in order to mimic the self-assembly properties of natural light-harvesting antennas and its self-assembly behaviour in solution and in solid state were studied by NMR and X-Ray spectroscopies. The self-assembly of this molecule was triggered in apolar solvents and studied in solution by UV-Vis spectroscopy, suggesting it is able to form slipped face-to-face aggregates, or J-aggregates. The nanoscopic and microscopic morphology of the aggregates was elucidated by atomic force microscopy, revealing the formation of extended two-dimensional structures
The importance of the electronic and steric features of the ancillary ligands on the rate of cis–trans isomerization of olefins coordinated to palladium(0) centre. A study involving (Z)-1,2-ditosylethene as olefin model
No full textWith the aim of better understanding the mechanisms governing the spontaneous cis–trans isomerization of the olefins promoted by palladium(0) centers, we have synthesized several novel complexes bearing (Z)- or (E)-1,2-ditosylethene and a combination of other two spectator ligands including phosphines (PPh3 and 1,3,5-triaza-7-phosphaadamantane), isocyanides (i.e. 2,6-dimethylphenylisocyanide) and Nheterocyclic carbenes (NHCs). The nature of ancillary ligands heavily influences the steric and electronic features of the metal centre and consequently its interaction with olefin determines a different capability of supporting the isomerization process. The kinetic analysis and the determination of the rate constants of the isomerization suggested that both the steric and electronic factors play an important role and only an unpredictable combination can guarantee the success of the reaction. The work is completed by the structural characterization of three different Pd(0) complexes
ACCEPTED ORAL CONTRIBUTION - “Linearly Polarized Infrared Investigations of Organic Semiconducting Single Crystals” - PRESENTING AUTHOR
No full textO-Annulation to Polycyclic Aromatic Hydrocarbons: A Tale of Optoelectronic Properties from Five- To Seven-Membered Rings
Full text linkWe take advantage of the Pummerer oxidative annulation reaction to extend PAHs through the formation of an intramolecular C-O bond with a suitable phenol substituent. Depending on the peripheral topology of the PAH precursor (e.g., pyrene, boron-dipyrromethene, or perylene diimide) five-, six-, and seven-membered O-containing rings could be obtained. The effect of the O-annulations on the optoelectronic properties were studied by various methods with the pyrano-annulated pyrene and BODIPY derivatives depicting quantitative emission quantum yields
Synthesis and characterization of novel olefin complexes of palladium(0) with chelating bis(N-heterocyclic carbenes) as spectator ligands
No full textWe have synthesized several novel palladium(0) olefin complexes stabilized by strong σ-donating bis-chelating carbene ligands characterized by one or two CH2 spacers and electron-withdrawing olefins. Although it appears obvious that the σ-donating carbenes and electron-withdrawing olefins should cooperate in the stabilization of the ensuing complexes, the limit of their coexistence was not hitherto clear. On the basis of previously measured stabilizing capability of the olefins toward Pd(0) complexes we were able to synthesize ten complexes (nine new and one synthesized by a different protocol from that of the literature). The less electron-withdrawing olefin capable of stabilizing the complex was dimethylfumarate. However, the most interesting results were obtained with the (Z)-1,2-bis(p-tolylsulfonyl)ethene (cis-sulf) which instantly isomerizes upon coordination and in the case of the derivative bearing the olefin tetramethyl ethene-1,1,2,2-tetracarboxylate (tmetc) whose decomposition in CD2Cl2 yields the saturated tetramethyl ethane-1,1,2,2-tetracarboxylate (D2). The solid-state structure of the complex 4d bearing the bis-carbene 1,1′-dibenzyl-3,3′methylenediimidazol-2,2′-diylidene and the olefin (E)-1,2-bis(p-tolylsulfonyl)ethene (trans-sulf) was also determined
Chemoselective oxidative addition of vinyl sulfones mediated by palladium complexes bearing picolyl-N-heterocyclic carbene ligands
No full textThe manifold interactions of (E)- or (Z)-1,2-ditosylethene with a palladium(0) centre bearing picolyl-NHC carbene ligands have been studied thoroughly. (E)-1,2-Ditosylethene produces the expected and stable η2-olefin palladium complexes, whereas the coordination of theZderivative alternatively promotes the isomerization of the olefin itself or an oxidative addition process depending on the steric bulkiness of carbene substituents and/or the adopted synthetic procedure. Remarkably, the oxidative addition pathway involves a selectiveS-vinyl (notS-aryl) breaking and produces selectively the S- rather than O-coordinated sulfinate. A mechanistic study has clarified the reasons of the chemoselectivity of the process, which was proved to be kinetically controlled. All the involved species have been isolated and exhaustively characterized. In particular, we report the first example of the X-ray crystal structure of a complex bearing one vinyl and one S-sulfinate fragment coordinated to palladium
Reactivity of N-heterocyclic carbene-pyridine palladacyclopentadiene complexes toward halogen addition. the unpredictable course of the reaction
No full textAs an extension of a previously published work we have reacted some palladacyclopentadiene complexes stabilized by bidentate N-heterocyclic carbene-pyridine or monodentate N-heterocyclic carbene-pyridine and isocyanide ligands with the halogens I2 and Br2. All the bidentate and monodentate complexes react with halogens to give at first the expected σ-coordinated butadienyl fragment. However, two of the less hindered NHC carbene-pyridine bidentate butadienyl iodo derivatives undergo a further rearrangement and novel Pd(ii) complexes characterized by a ten term coordinative ring were isolated and characterized. In the most favorable case we were able to carry out the kinetics of rearrangement and measure its reaction rate. Moreover, we have surmised a plausible mechanism on the basis of a dedicated computational approach and in one case the surprising structure characterized by the ten term coordinative ring was resolved by X-ray diffraction
Heliophyllite: A discredited mineral species identical to ecdemite
Full text linkThe type material for heliophyllite, preserved in the Swedish Museum of Natural History in Stockholm, was re-investigated through a combined EPMA (electron probe X-ray microanalysis), Raman, and X-ray powder diffraction (XRPD) and single-crystal study. EPMA chemical data, together with Raman and single-crystal structural studies, point to heliophyllite being identical to ecdemite. XRPD synchrotron data highlight the presence of a minor quantity of finely admixed finnemanite in the analyzed material, explaining the presence of some additional diffraction peaks, not indexable with the ecdemite unit cell, reported in the literature. The discreditation of heliophyllite has been approved by the IMA Commission on New Minerals and Mineral Names (proposal 19-H, 2019)
Synthesis and characterization of novel olefin complexes of palladium(0) with chelating bis(N-heterocyclic carbenes) as spectator ligands
Full text linkWe have synthesized several novel palladium(0) olefin complexes stabilized by strong σ-donating bis-chelating carbene ligands characterized by one or two CH2spacers and electron-withdrawing olefins. Although it appears obvious that the σ-donating carbenes and electron-withdrawing olefins should cooperate in the stabilization of the ensuing complexes, the limit of their coexistence was not hitherto clear. On the basis of previously measured stabilizing capability of the olefins toward Pd(0) complexes we were able to synthesize ten complexes (nine new and one synthesized by a different protocol from that of the literature). The less electron-withdrawing olefin capable of stabilizing the complex was dimethylfumarate. However, the most interesting results were obtained with the (Z)-1,2-bis(p-tolylsulfonyl)ethene (cis-sulf) which instantly isomerizes upon coordination and in the case of the derivative bearing the olefin tetramethyl ethene-1,1,2,2-tetracarboxylate (tmetc) whose decomposition in CD2Cl2yields the saturated tetramethyl ethane-1,1,2,2-tetracarboxylate (D2). The solid-state structure of the complex 4d bearing the bis-carbene 1,1′-dibenzyl-3,3′methylenediimidazol-2,2′-diylidene and the olefin (E)-1,2-bis(p-tolylsulfonyl)ethene (trans-sulf) was also determined
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