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Mono- and Bimetallic Zwitterionic Chromium(0) and Tungsten(0) Allenyls
2015
A series of stable chiral (racemic), formally neutral, zwitterionic mono- and bimetallic M(CO)5[C(OEt)═C═CR(NHC)] (M = Cr, W) σ-allenyls are ready available by the addition of N-heterocyclic carbenes (NHCs) to Cr(0) and W(0) alkynyl Fischer carbene complexes. Different classes of NHCs, (e.g., 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene, and their six- and seven-membered analogues and 1,3-bis(dimethyl)imidazol-2-ylidene) were employed as nucleophiles in these C-C bond-forming reactions yielding the novel complexes in essentially quantitative yields. A systematic experimental and computational study of the electronic properties of the C…
Cu2+-Induced formation of cage-like compounds containing pyrazole macrocycles
2002
The crystal structure of the complex [Cu4(H22L)2(H2O)2- (ClO4)2](ClO4)2·2H2O where L is a new pyrazole ligand containing 1,5-diaminopentane spacers represents a new form of obtaining metal ion-induced inorganic–organic cages. Escarti Alemany, Francisco, franesa@alumni.uv.es ; Latorre Saborit, Julio, Julio.Latorre@uv.es ; Garcia-España Monsonis, Enrique, Enrique.Garcia-Es@uv.es
Azide bridged dicopper(II), dicobalt(II) complexes and a rare double μ-chloride bridged ferromagnetic dicobalt(II) complex of a pyrazolyl-pyrimidine …
2012
Abstract Two new dinuclear copper(II) complexes [Cu2(PymPz)2(N3)2Cl2] (1), [Cu2(PymPz)2(N3)4] (2) and two new dinuclear cobalt(II) complexes [Co2(PymPz)2Cl4] (3), [Co2(PymPz)2(N3)4] (4) [PymPz = 2-(3,5-dimethyl-1H-pyrazol-1-yl)-4,6-dimethylpyrimidine] have been synthesized and characterized crystallographically and spectroscopically. In each of the complexes 1, 2 and 4 the two adjacent metal centers are bridged by a pair of μ-1,1 azide groups whereas in 3 the metal centers are bridged by a pair of chloride ions. In the complexes, all the metal centers are pentacoordinated. In 1 and 2 the copper(II) centers have distorted square pyramidal geometry (τ = 0.18 for 1 and 0.091 for 2) but in 3 an…
Double azido-bridged and mixed-bridged binuclear copper(II) and nickel(II) compounds with N,N,O-donor Schiff bases: Synthesis, structure, magnetic an…
2015
Abstract Two dinuclear complexes μ1,1-azido bridged [Cu(L1)(N3)]2 (1) and μ-phenoxo, μ1,1-azido bridged [Ni2(L2)2(μ1,1-N3)(N3) H2O] (2) bearing HL1 and HL2 as a blocking co-ligands produced by the 1:1 condensation of N-benzyl ethylenediamine with ortho-hydroxy acetophenone and N-methyl propanediamine with 3-methoxy salicylaldehyde respectively, have been synthesized and successfully characterized by elemental analyses, IR and electronic spectroscopy, single-crystal X-ray diffraction, variable temperature magnetic study and DFT studies. X-ray crystal structures of 1 reveal that the Cu(II) ion displays a five-coordinate square pyramidal coordination with a centro-symmetric μ1,1-azido bridging…
Fluoroquinolone–metal complexes: A route to counteract bacterial resistance?
2014
Abstract Microbial resistance to antibiotics is one of the biggest public health threats of the modern world. Antibiotic resistance is an area of much clinical relevance and therefore research that has the potential to identify agents that may circumvent it or treat resistant infections is paramount. Solution behavior of various fluoroquinolone (FQ) complexes with copper(II) in the presence and absence of 1,10-phenanthroline (phen) was studied in aqueous solution, by potentiometry and/or spectrophotometry, and are herein described. The results obtained showed that under physiological conditions (micromolar concentration range and pH 7.4) only copper(II):FQ:phen ternary complexes are stable.…
A new tetranuclear copper(I) complex based on allyl(5-phenyl-1,3,4-thiadiazol-2-yl)azanide ligand: Synthesis and structural characterization
2015
Abstract By means of alternating current electrochemical technique a new tetranuclear crystalline copper(I) complex [Cu I 4 ( L − ) 4 ] ( L − – allyl(5-phenyl-1,3,4-thiadiazol-2-yl)azanide ion) has been obtained and characterized by X-ray single crystal diffraction ( Sp. gr. I 4 1 / a ) and Raman spectroscopy. The metal center adopts linear arrangement, composed of one thiadiazole N atom from the one L − anion and one azanide N atom of the other L − ligand. A bridged Cu atoms stitch four L − ligands into the firstly observed tetranuclear copper(I) azanide complex with intramolecular Cu(I)⋯Cu(I) interactions at the distance of 2.7451(6) A. Molecular structure and Raman spectrum of the compo…
Rare-earth metal bis(tetramethylaluminate) complexes supported by a sterically crowded triazenido ligand
2010
Complexes [NNN]Ln(AlMe(4))(2) (Ln = Y, La, Nd, Lu) bearing the sterically demanding aryl-substituted triazenido ligand [(Tph)(2)N(3)] (Tph = [2-(2,4,6-iPr(3)C(6)H(2))C(6)H(4)]) can be obtained from homoleptic complexes Ln(AlMe(4))(3) in moderate yields, both via protonolysis with [(Tph)(2)N(3)]H and a salt metathesis reaction pathway utilizing [(Tph)(2)N(3)]K. In the solid state the Y and Lu derivatives are isostructural, with both tetramethylaluminate groups coordinated in an eta(2) fashion, while one of the [AlMe(4)] ligands of the Nd derivative features a distorted eta(2) coordination mode. Due to the high affinity of the triazenido ligand toward the more Lewis-acidic and harder aluminiu…
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.