Search results for "medium"
showing 10 items of 3746 documents
Ethylene oligomerization with 2-hydroxymethyl-5,6,7-trihydroquinolinyl-8-ylideneamine-Ni(II) chlorides
2021
Abstract A series of Ni complexes of the general formula [2-(MeOH)-8-{N(Ar)}C9H8N]NiCl2, where Ar = 2,6-Me2C6H3 in Ni1; 2,6-Et2C6H3 in Ni2; 2,6-i-Pr2C6H3 in Ni3; 2,4,6-Me3C6H2 in Ni4; 2,6-Et2-4-MeC6H2 in Ni5 and 2,4,6-t-Bu3C6H2 in Ni6 has been synthesized and characterized by elemental analysis and IR spectroscopy. On activation with MMAO or Et2AlCl, these complexes showed high activity in ethylene oligomerization, reaching 2.23 × 106 g·mol–1 (Ni) h–1 at 30 °C with the Al/Ni ratio of 5500 and 9.11 × 105 g·mol–1 (Ni) h–1 with the Al/Ni of 800, respectively. Moreover, the content of α-C4 indicated high selectivity exceeding 99% in the Ni/Et2AlCl system. Comparing with the previous report by o…
Hydrogenation of acetylene-ethylene mixtures on Pd catalysts: study of the surface mechanism by computational approaches. Metal dispersion and cataly…
2000
The hydrogenation mechanism of acetylene–ethylene mixtures on Pd catalysts under different experimental conditions was studied by employing a time-dependent Monte Carlo approach set to use a fixed series of event probabilities. The dependence of the catalyst activity and selectivity on the sizes of the metal particles was simulated at microscopic level and the results, also refined by fitting procedures, suggested proper explanations for the apparent nonuniformity of the related experimental findings. The use of the steric hindrance parameter of the surface species and the available surface energy on the metallic catalyst sites was decisive for reproducing the experimental results.
ChemInform Abstract: Synthesis and Functionalization of Chalcogenide Nanotubes
2011
New synthetic approaches to MS 2 (M = Sn, Nb, Mo, W) chalcogenide nanostructures are highlighted. Most chalcogenide particles can be functionalized directly with inorganic nanoparticles such as Au, ZnO or MnO. Depending on the Pearson hardness of the metal involved, the functionalization may be reversible or irreversible. A covalent functionalization strategy is based on a steric shielding of the coordination sphere of transition metal atoms in such a way that only coordination sites are available for bonding to the chalcogenide surface. This allows the immobilization of fluorophors, redox active groups or proteins onto chalcogenide nanoparticle.
Synthesis and functionalization of chalcogenide nanotubes
2010
New synthetic approaches to MS 2 (M = Sn, Nb, Mo, W) chalcogenide nanostructures are highlighted. Most chalcogenide particles can be functionalized directly with inorganic nanoparticles such as Au, ZnO or MnO. Depending on the Pearson hardness of the metal involved, the functionalization may be reversible or irreversible. A covalent functionalization strategy is based on a steric shielding of the coordination sphere of transition metal atoms in such a way that only coordination sites are available for bonding to the chalcogenide surface. This allows the immobilization of fluorophors, redox active groups or proteins onto chalcogenide nanoparticle.
Binding abilities of dehydropeptides towards Cu(II) and Ni(II) ions. Impact of Z–E isomerization on metal ion binding
2002
The study on the binding ability of dehydro-tri- and tetrapeptides has shown that the alpha,beta-double bond has a critical effect on the peptide coordination to metal ions. It may affect the binding of the vicinal amide nitrogens by the electronic effect and stabilize the complex due to steric effects. The (Z) isomer is the most effective in stabilizing of the complexes formed. The presence of large side chain in the dehydroamino acid residue may also be critical for the coordination mode in the metallopeptide systems.
Modeling Supramolecular Polymerization: The Role of Steric Effects and Hydrophobic Interactions
2019
We present a combined experimental–simulation study of self-assembly into one-dimensional filaments. Experimentally, we study amphiphilic AuI-metallopeptides in neutral aqueous media. Our model foc...
Contact formation in random networks of elongated objects
2014
The effect of steric hindrance is an important aspect of granular packings as it gives rise to, e.g., limitations on the densities of ordered and disordered packings, both of which are essentially defined by the geometry of the constituents. Here we focus on the random packing of rods via deposition and their distributions of contact number and segment length. Such statistical properties are relevant for mechanical properties of the structures, but the (quite large) steric effects on them have not been addressed in previous studies. We therefore develop a theory that describes the statistical properties of rod packings, while taking into account that the deposited rods cannot overlap and th…
Tin( II ) and Lead( II ) 4‐Acyl‐5‐pyrazolonates: Synthesis, Spectroscopic and X‐ray Structural Characterization
2004
Novel tin(II) β-diketonate Sn(Q)2 complexes [HQ = 1-R1-3-R3-4-R4(C=O)-pyrazol-5-one; HQC: R1 = Ph, R3 = Me, R4 = Cy; HQS: R1 = Ph, R3 = Me, R4 = CHPh2; HQL: R1 = Ph, R3 = Me, R4 = CH2Ph; HQT: R1 = Ph, R3 = Me, R4 = CH2tBu; HQE: R1 = Ph, R3 = Me, R4 = Et; HQB: R1 = Ph, R3 = Me, R4 = tBu; HQW: R1 = Ph, R3 = Me, R4 = p-(tBu)Ph; HQR: R1 = Ph, R3 = Me, R4 = p-[(CH2)5CH3]Ph; HQN: R1 = p-NO2Ph, R3 = Me, R4 = Ph; HQM: R1 = Me, R3 = Me, R4 = Ph; HQD: R1 = Me, R3 = Me, R4 = Me; HQP: R1 = Ph, R3 = Ph, R4 = Ph; HQG: R1 = Ph, R3 = Ph, R4 = Me; HQF: R1 = p-CF3Ph, R3 = Me, R4 = Ph; HQH: R1 = p-CF3Ph, R3 = Me, R4 = Me] have been isolated and characterized by single-crystal X-ray diffraction analyses, IR, 1…
Triphosphine-supported bimetallic Au(I)-M(I) (M = Ag, Cu) alkynyl clusters.
2014
The reactions of gold acetylides (AuC2R)n with triphosphine ligands PPh2-(CH2)n-PPh-(CH2)2-PPh2 (n = 1, dpmp; 2, dpep) in the presence of M(+) ions (M = Cu, Ag) lead to an assembly of the heterometallic clusters, the composition of which is determined by the steric bulkiness of the alkynyl groups and the flexibility of the phosphine motifs. For R = Ph, an unprecedented hexanuclear complex [Au5Cu(C2R)4(dpmp)2](2+) (1) was isolated, while for the aliphatic alkynes (R = 1-cyclohexanolyl, 2-borneolyl, 2,6-dimethyl-4-heptanolyl) a family of compounds based on a tetrametallic framework was prepared, [Au3Cu(C2R)3(dpmp)](+) (2, R = 1-cyclohexanolyl), [Au3M(C2R)3(dpep)]2(+2) (3, M = Cu, R = 1-cycloh…
Unique distal size selectivity with a digold catalyst during alkyne homocoupling
2015
Metal-catalysed chemical reactions are often controlled by steric hindrance around the metal atom and it is rare that substituents far away of the reaction site could be differentiated during reaction, particularly if they are simple alkyl groups. Here we show that a gold catalyst is able to discriminate between linear carbon alkynes with 10 or 12 atoms in the chain during the oxidative homocoupling of alkynes: the former is fully reactive and the latter is practically unreactive. We present experimental evidences, which support that the distal size selectivity occurs by the impossibility of transmetallating two long alkyl chains in an A-framed, mixed-valence digold (I, III) acetylide compl…