Search results for "Effects"
showing 10 items of 2634 documents
The Instability of Ni{N(SiMe3 )2 }2 : A Fifty Year Old Transition Metal Silylamide Mystery.
2015
The characterization of the unstable Ni(II) bis(silylamide) Ni{N(SiMe3 )2 }2 (1), its THF complex Ni{N(SiMe3 )2 }2 (THF) (2), and the stable bis(pyridine) derivative trans-Ni{N(SiMe3 )2 }2 (py)2 (3), is described. Both 1 and 2 decompose at ca. 25 °C to a tetrameric Ni(I) species, [Ni{N(SiMe3 )2 }]4 (4), also obtainable from LiN(SiMe3 )2 and NiCl2 (DME). Experimental and computational data indicate that the instability of 1 is likely due to ease of reduction of Ni(II) to Ni(I) and the stabilization of 4 through dispersion forces.
Stereocontrol in Diphenylprolinol Silyl Ether Catalyzed Michael Additions : Steric Shielding or Curtin-Hammett Scenario?
2017
The enantioselectivity of amine-catalyzed reactions of aldehydes with electrophiles is often explained by simple steric arguments emphasizing the role of the bulky group of the catalyst that prevents the approach of the electrophile from the more hindered side. This standard steric shielding model has recently been challenged by the discovery of stable downstream intermediates, which appear to be involved in the rate-determining step of the catalytic cycle. The alternative model, referred to as Curtin-Hammett scenario of stereocontrol, assumes that the enantioselectivity is related to the stability and reactivity of downstream intermediates. In our present computational study, we examine th…
Exceedingly Fast Oxygen Atom Transfer to Olefins via a Catalytically Competent Nonheme Iron Species
2016
El mateix article està publicat en alemany a l'edició alemanya d' 'Angewandte Chemie' (ISSN 0044-8249, EISSN 1521-3757), 2016, vol. 128, núm. 21, p.6418–6422. DOI http://dx.doi.org/10.1002/ange.201601396 The reaction of [Fe(CF3SO3)2(PyNMe3)] with excess peracetic acid at −40 °C leads to the accumulation of a metastable compound that exists as a pair of electromeric species, [FeIII(OOAc)(PyNMe3)]2+ and [FeV(O)(OAc)(PyNMe3)]2+, in fast equilibrium. Stopped-flow UV/Vis analysis confirmed that oxygen atom transfer (OAT) from these electromeric species to olefinic substrates is exceedingly fast, forming epoxides with stereoretention. The impact of the electronic and steric properties of the subs…
Halogen...halogen interactions in pressure-frozen ortho- and meta-dichlorobenzene isomers.
2007
Isomers 1,2-dichlorobenzene (o-DCB) and 1,3-dichlorobenzene (m-DCB) were high-pressure frozen in-situ in a Merrill–Bassett diamond–anvil cell and their structures determined at room temperature and at 0.18 (5) GPa for o-DCB, and 0.17 (5) GPa for m-DCB by single-crystal X-ray diffraction. The patterns of halogen...halogen intermolecular interactions in these structures can be considered to be the main cohesive forces responsible for the molecular arrangements in these crystals. The molecular packing of dichlorobenzene isomers, including three polymorphs of 1,4-dichlorobenzene (p-DCB), have been compared and relations between their molecular symmetry, packing arrangements, intermolecular inte…
Molecular association of small amphiphiles: Origin of ionic liquid properties in dibutyl phosphate/propylamine binary mixtures
2018
Abstract Binary mixtures of liquid surfactants, owing to the amphiphilic nature of the molecules involved, can exhibit nano-segregation and peculiar transport properties. The amphiphilicity, and consequently the resulting self-assembly, can be tuned by changing the length of the alkyl chains and the nature of the polar head group. So, in the present study, the structural and dynamic properties of dibutyl phosphate/propylamine liquid mixtures at various compositions have been investigated by Wide Angle X-ray Scattering (WAXS), FT-IR, rheometry and dielectric spectroscopy in order to study the intermolecular association taking place when alkylphosphates and alkylamines with a small apolar par…
Tetrameric and Dimeric [N∙∙∙I+∙∙∙N] Halogen-Bonded Supramolecular Cages
2017
Tripodal N-donor ligands are used to form halogen-bonded assemblies via structurally analogous Ag+-complexes. Selective formation of discrete tetrameric I6L4 and dimeric I3L2 halonium cages, wherein multiple [N∙∙∙I+∙∙∙N] halogen bonds are used in concert, can be achieved by using sterically rigidified cationic tris(1-methyl-1-azonia-4-azabicyclo[2.2.2]octane)-mesitylene ligand, L1(PF6)3, and flexible ligand 1,3,5-tris(imidazole-1-ylmethyl)-2,4,6-trimethylbenzene, L2, respectively. The iodonium cages, I6L14(PF6)18 and I3L22(PF6)3, were obtained through the [N∙∙∙Ag+∙∙∙N] → [N∙∙∙I+∙∙∙N] cation exchange reaction between the corresponding Ag6L14(PF6)18 and Ag3L22(PF6)3 coordination cages, prepar…
Thiophene based imino-pyridyl palladium(II) complexes : Synthesis, molecular structures and Heck coupling reactions
2017
Abstract The new compounds (5-methyl-2-thiophene-2-pyridyl(R))imine [R = methyl (L1); R = ethyl (L2)] and (5-bromo-2-thiophene-2-pyridyl(R)imine [R = methyl (L3); R = ethyl (L4)] were successfully synthesized via Schiff base condensation reaction and obtained in good yields. These potential ligands were reacted with [PdCl2(COD)] and [PdClMe(COD)] to give the corresponding complexes [PdCl2(L)] (L = L1-L4; 1–4) and [PdClMe(L)] (L = L1-L4; 5–8). All compounds were characterized by IR, 1H and 13C NMR spectroscopy, elemental analysis and mass spectrometry. The molecular structures of 1, 2, 6 and 8 were confirmed by X-ray crystallography. The complexes were evaluated as catalyst precursors for st…
Photo‐Induced Polymerization and Stress Effects in Fullerite C60
2005
Abstract Modifications of the structure and hardness of fullerite C60 crystals under stresses generated during photo‐induced polymerization are investigated.
Fine–grained spinel ferrites: From the reactivity to magnetic properties
1998
The oxidation at low temperature of fine-grained ferrites containing oxidizable cations such as Cu + , Fe 2+ , Mn 2+ , Mo 3+ , V 3+ , has led to new mixed-valent cation deficient ferrites with a large number of vacancies. It has been demonstrated by DTG analysis that each cation oxidizes at a specific temperature in close relation with the cation-oxygen distance. The kinetics oxidation of each oxidizable cation has been explained on the basis of a diffusion-induced stress effect when these stresses are generated by the chemical gradient induced during the oxidation process. When fine-grained ferrites contain some Co-cations, it has been revealed that the stresses have a significant influenc…
Pesticide Effects on Eel Metabolism
1995
Previous works on endosulfan eel toxicology in this laboratory demonstrated that 0.041 mg/liter of endosulfan was the 50% lethal concentration of 96 hr exposure. Eels of species Anguilla anguilla were exposed to two sublethal endosulfan concentrations: 8.2 μg/liter (1/5 LC50) and 4.1 μg/liter (1/10 LC50), and the experiment was done at different exposure times: 12, 24, 48, 72, and 96 hr. Muscle glycogen content decreased significantly (P < 0.05) at 24, 48, 72, and 96 hr exposure to 8.2 μg/liter pesticide; levels did not decline at any time when animals were exposed to 4.1 μg/liter. Muscle lactate levels in fish did not change significantly while lactate levels in eel blood increased at 12, …