Asymmetric cyclization of omega-formyl-1,3-dienes catalyzed by a zerovalent nickel complex in the presence of silanes

A nickel(0)-catalyzed asymmetric cyclization of omega-formyl-1,3-diene in the presence of silanes in which five- or six-membered carbocycles or pyrrolidine derivatives were afforded up to 86% ee by the use of (2R,5R)-2,5-dimethyl-1-phenylphospholane as a monodentate chiral ligand was investigated. The reaction course of this asymmetric cyclization can be explained for by two possible mechanisms: one in which the cyclization proceeds via a pi-allylnickel intermediate to produce a cyclized product having an internal olefin in the side chain, and one in which the cyclization proceeds via a sigma bond metathesis of silane and the nickel-oxygen bond of oxanickelacycle to produce a cyclized compound having a terminal olefin and/or an internal olefin in the side chain. It was speculated that both of these mechanisms operate in this asymmetric cyclization depending upon the nature of silanes and the reaction conditions.     

Enhancement of the electrochemical reduction of oxygen at platinum by nickel underpotential deposition

Polycrystalline Pt electrode was modified by underpotential deposition (upd) of nickel. The modification was performed by potential cycling in phosphate buffer pH 7. 0 containing NiSO₄, in which hydrogen and nickel upd processes were well separated. The maximum Ni upd coverage was found to be 0.3. Oxygen reduction was studied at bare and nickel upd-modified Pt. It was found that the reaction rate increased with increasing Ni upd coverage. At θ(Ni)=0.3, the current density was a factor of 2 higher compared to bare Pt (at the potential of 0.85 V). The capacitance of the electrode interface was determined in potential-relaxation experiments following interruption of the polarization current. It was found that the pseudocapacitance owing to a coverage by the adsorbed reaction intermediates was higher on the Ni-modified Pt surface than on bare Pt, which resulted in higher reaction rate. The influence of Ni adatoms on the surface coverage by the reaction intermediates was attributed to the inhibition of OH adsorption on Pt by OH ligands attached on neighboring Ni atoms.     

Preparation, electrochemical and spectral properties of N-methyl-pyridylethynyl nickel porphyrins

A series of nickel N-methyl-pyridylethynylporphines were synthesized and their electrochemical and absorption properties were studied. UV-visible spectra of these complexes show that the absorption red-shifts of the nickel porphyrins are as significant as the zinc analogues. Although the reduction potential shifts caused by the electron-withdrawing substituents are not as large as the zinc complexes, the first reduction potentials of the nickel porphyrins are more positive than those of the zinc counterparts. In addition, the redox behaviors of these nickel porphyrins are similar to those of the zinc analogues.     

An electroactive nickel containing polymeric film obtained by electrochemical reduction of an aryl-nickel derivative

The electrochemical reduction of [Ni(PPh₃)₂(p-C₆H₄Br)Br] in acetonitrile results in a polymeric coating of a nickel-containing poly-p-phenylene, formulated as [-Ni(p-C₆H₄)_n-] (n=6?7) on the basis of elemental analysis, IR, UV, MS and ESCA measurements. This coating is found to undergo a two-electron reversible reduction and a one-electron reversible oxidation with a large potential window (3.6 V), without the polymeric film being destroyed. Moreover, the polymer obtained is shown to be electroactive towards dissolved reactants via permeation or mediated electron transfer, depending on the molecular size of the electroactive species employed.     

Living radical polymerization of methyl methacrylate with a zerovalent nickel complex,Ni(PPh3)

A zerovalent nickel complex, Ni(PPh₃)₄, induced living radical polymerization of methyl methacrylate (MMA) in conjunction with an organic bromide as an initiator [R–Br: CCl₃Br, (CH₃)₂C(CO₂Et)Br, (CH₃)₂C(COPh)Br] in the presence of Al(Oi-Pr)₃ additive. The molecular weight distributions were narrow (M̄_w/M̄_n ∼ 1.2) throughout the reactions, and the number-average molecular weights (M̄_n) increased in direct proportion to monomer conversion. In contrast, the polymers obtained with CCl₄ in place of R–Br had broader MWDs (M̄_w/M̄_n > 2). The Al(Oi-Pr)₃ additive should be added for the smooth polymerizations of MMA to occur, similarly to those with a divalent nickel bromide, NiBr₂(PPh₃)₂. The Ni(PPh₃)₄-mediated living polymerization apparently proceeds via the activation of the C Br bond from the initiators R Br, assisted by the redox reaction of the complex between Ni(0) and Ni(I) species. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3003–3009, 1999     

Preparation and electrochemical behavior of a macrocyclic heterodinuclear FeIIICoIII complex

A new macrocyclic heterodinuclear Fe^IIICo^III complex, prepared by the condensation of 2,6-diformylpyridine N-oxide with 1,3-diaminopropane in the presence of FeCl₂.4H₂O and CoCl₂.6H₂O, and formulated as FeCoLCl₆.C₂H₅OH.8H₂O, was characterized by elemental analyses, IR and Mössbauer spectra and investigated electrochemically on an ultramicrodisk platinum electrode. The results show that the electrode reaction can be thought as a nearly reversible transfer process. The diffusion coefficient is 1.93×10^-6 m² s^-1 and E^o ̄ is −0.229V (versus s.c.e) and α=0.877. The average electron transfer rate constant k^o′ is 3.21×10^-3 cm s^-1.     

Synthesis and electrochemical characterization of carbon nanotubes decorated with nickel nanoparticles for use as an electrochemical capacitor

Attachment of nickel nanoparticles on multiwalled carbon nanotubes (MWCNTs) was conducted to explore the influence of Ni loading on the electrochemical capacitance of MWCNT electrodes. A chemical impregnation leaded to homogeneously disperse Ni particles onto the surface of MWCNTs, and the Ni particles were found to be an average size of 30–50 nm. The capacitive behavior of the MWCNT electrodes was investigated in 6 M KOH, by using cyclic voltammetry (CV), charge–discharge cycling, and ac electrochemical impedance spectroscopy. CV measurements showed that the Faradaic current was found to increase with the Ni coverage, indicating that the presence of Ni would enhance the pseudocapacitance through the redox process. Equivalent circuit analysis indicated that both of electrical connection and charge transfer resistances accounted for the major proportion of the overall resistance and were found to decrease with the amount of nickel. A linearity relationship between the total capacitance and the Ni population reflected that each Ni particle exhibits an identical electrochemical activity in enhancing the electrochemical capacitance. The overall electrochemical capacitance (including double layer capacitance and pseudocapacitance) of Ni-MWCNT electrode can reach a maximum of 210 F/g over 500 cycles.     

Preparation of hexagonal nanoporous nickel hydroxide film and its application for electrochemical capacitor

Nanoporous nickel hydroxide film has been successfully electrodeposited on titanium substrate from nickel nitrate dissolved in the aqueous domains of the hexagonal lyotropic liquid crystalline phase of Brij 56. Low-angle X-ray diffraction (XRD), transmission electron microscopy (TEM), and atomic force microscopy (AFM) studies show that the film has a regular nanostructure consisting of a hexagonal array of cylindrical pores with a repeat center-to-center spacing of about 7 nm. Preliminary electrochemical studies are carried out using cyclic voltammetry (CV) and chronopotentiometry technology. A maximum specific capacitance of 578 F g⁻¹ could be achieved for the nanoporous Ni(OH)₂ film electrode, suggesting its potential application in electrochemical capacitors.     

Elaborately tuning the electronic structure of single-atom nickel sites using nickel nanoparticles to markedly enhance the electrochemical reduction of nitrate into ammonia

The electrochemical reduction of nitrate to ammonia(NH₃) can be used to recycle nitrogen and offers a decarbonized route for sustainable NH₃ production,but requires efficient electrocatalysts.Herein,we have rationally designed and fabricated a novel self-supported electrocatalyst comprised of Ni nanoparticles(Ni_NPs) embedded in Ni single atoms(Ni_SAs) anchored to nitrogen-doped carbon nanotubes grown on carbon cloth(Ni_NPs@Ni_SAs-NCN...     

The catalysis of the electrochemical reduction of alkyl bromides by nickel complexes: The formation of carboncarbon bonds

The square planar, macrocyclic nickel complex, N, N′-ethylenebis(salicylideneiminato)nickel(II), is shown to be an effective catalyst for the electrochemical reduction of substituted alkyl bromides; this indirect cathodic reduction can lead to a good yield of dimeric products. The reduction of alkyl bromides in the presence of an activated olefin is shown to lead to mixtures of products compatible with radical addition to the double bond. The mechanism of the reaction of nickel(I) complexes with alkyl bromides is discussed in the light of these results.     

Preparation of selenides of copper,cadmium, cobalt and nickel by the reduction of selenites in aqueous solutions

Conclusions On the example of the reduction of the selenious salts of Cu, Cd, Co and Ni it was shown that selenides of stoichiometric composition can be obtained by the reduction of selenites with sodium hydrosulfite in alkaline medium.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 934–935, May, 1966.     

Experimental and theoretical examination of C-CN and C-H bond activations of acetonitrile using zerovalent nickel

Experimental and density functional theory show that the reaction of acetonitrile with a zerovalent nickel bis(dialkylphosphino)ethane fragment (alkyl = methyl, isopropyl) proceeds via initial exothermic formation of an eta(2)-nitrile complex. Three well-defined transition states have been found on the potential energy surface between the eta(2)-nitrile complex and the activation products. The lowest energy transition state is an eta(3)-acetonitrile complex, which connects the eta(2)-nitrile to a higher energy eta(3)-acetonitrile intermediate with an agostic C-H bond, while the other two lead to cleavage of either the C-H or the C-CN bonds. Gas-phase calculations show C-CN bond activation to be endothermic, which contradicts the observation of thermal C-CN activation in THF. Therefore, the effect of solvent was taken into consideration by using the polarizable continuum model (PCM), whereupon the activation of the C-CN bond was found to be exothermic. Furthermore the C-CN bond activation was found to be favored exclusively over C-H bond activation due to the strong thermodynamic driving force and slightly lower kinetic barrier.     

Preparation of DNA-silver nanohybrids in multilayer nanoreactors by in situ electrochemical reduction, characterization, and application

Novel nanocomposite films containing DNA-silver nanohybrids have been successfully fabricated by combined use of the layer-by-layer self-assembly technique and an in situ electrochemical reduction method with the DNA-Ag+ complex as one of the building blocks. UV-vis absorption spectroscopy was employed to monitor the buildup of the multilayer films, which suggested a progressive deposition with almost an equal amount of the DNA-Ag+ complex in each cycle. The following electrochemical reduction of silver resulted in the formation of metal nanoparticles in the film, which was evidenced by the evolution of the intense plasmon absorption band originating from silver. Scanning electron microscopy indicated that the particles formed in the multilayer films possessed good monodispersity and stability, thanks to the surrounding polymers. X-ray photoelectron spectroscopy further confirmed the presence of the main components (such as DNA and metallic silver) of the nanocomposite films. In addition, we show that the size of the metal nanoparticles and the optical property of the film could be readily tuned by manipulating the assembly conditions. Furthermore, the feasibility of the as-prepared nanocomposite films functioning as a surface-enhanced Raman scattering active substrate for sensing purposes was investigated, and the results showed great enhancement of the Raman signal of two probe molecules, Rhodamine 6G and 4-aminothiophenol.     

Preparation of dendritic nanoporous Ni-NiO foam by electrochemical dealloying for use in high-performance supercapacitors

Journal of Solid State Electrochemistry - This paper compared the applicability of nickel-copper and nickel-nickel oxide metallic foams as current collectors for supercapacitor. A comprehensive...     

Complexing influence of cobalt and nickel ions on the electrochemical reduction of pterin and related compounds at a mercury drop

The effect of Co(2+) and Ni(2+) ions on the electrochemical reduction of pterin and its derivatives, pteroic and pteroylmonoglutamic acids, has been studied. The measurements were carried out in aqueous solutions at fixed pH (7.5 +/- 0.2), temperature (298 +/- 0.2 K) and ionic strength (mu = 1.00; NaClO(4)) using polarographic techniques. By employing cyclic voltammetry and differential pulse polarography displacements were determined of the half-wave potentials E (1 2 ) of ligands of the reducible organic compounds at a dropping mercury electrode. The recorded polarograms and inherent potential differences were then utilized to calculate conditional stability constants of the complexes. The Casassas-Eek method was employed for the interpretation of the potential differences of the free and complexed ligands. The log beta(1) values of the stability constants revealed moderate stability of the complexes. The donor atoms of the ligands in the coordination compounds have also been identified.     

Surface modification by electrochemical reduction of alkyldiazonium salts

Since alkyldiazonium salts are highly unstable, their grafting is not as easy as that of aryldiazonium salts. However, it is possible to graft alkyl chains on copper electrodes by the in situ reaction of alkyl amines dissolved in aqueous perchloric acid with nitrite ions electrogenerated from nitrate ions.     

Preparation, structure, and dynamics of a nickel π-allyl cyanide complex

The complex (dippe)Ni(η³-allyl)(CN) has been prepared and fully characterized (dippe=bis-(diisopropylphosphino)ethane), including X-ray diffraction studies, as a square pyramidal structure. The complex shows dynamic ¹H-NMR behavior consistent with substantial structural rearrangements upon π to σ allyl interconversion. A comparison is made with (dippe)Ni(η³-allyl)Br, which also displays a square pyramidal structure.