Nickel(II) meso-hydroxyporphyrin complexes revisited: Palladium-catalysed synthesis, electronic structures of derived oxy radicals, and oxidative coupling to a dioxoporphodimethene dyad

We report the synthesis and characterisation of new examples of meso-hydroxynickel(II) porphyrins with 5,15-diphenyl and 10-phenyl-5,15-diphenyl/diaryl substitu- tion. The OH group was introduced by using carbonate or hydroxide as nucleophile by using palladium/phosphine cat- alysis. The NiPor OHs exist in solution in equilibrium with the corresponding oxy radicals NiPor OC. The 15-phenyl group stabilises the radicals, so that the 1H NMR spectra of {NiPor OH} are extremely broad due to chemical exchange with the paramagnetic species. The radical concentration for the diphenylporphyrin analogue is only 1%, and its NMR line-broadening was able to be studied by variable-tempera- ture NMR spectroscopy. The EPR signals of NiPor OC are con- sistent with somewhat delocalised porphyrinyloxy radicals, and the spin distributions calculated by using density func- tional theory match the EPR and NMR spectroscopic obser- vations. Nickel(II) meso-hydroxy-10,20-diphenylporphyrin was oxidatively coupled to a dioxo-terminated porphodimethene dyad, the strongly red-shifted electronic spectrum of which was successfully modelled by using time-dependent DFT calculations.

A Unique Nickel System having Versatile Catalytic Activity of Biological Significance

A new dinuclear nickel(II) complex, [Ni-2(LH2)(H2O)(2)(OH)(NO3)](NO3)(3) (1), of an "end-off" compartmental ligand 2,6-bis(N-ethylpiperazine-iminomethyl)-4-methyl-phenolato, has been synthesized and structurally characterized. The X-ray single crystal structure analysis shows that the piperazine moieties assume the expected chair conformation and are protonated. The complex 1 exhibits versatile catalytic activities of biological significance, viz. catecholase, phosphatase, and DNA cleavage activities, etc. The catecholase activity of the complex observed is very dependent on the nature of the solvent. In acetonitrile medium, the complex is inactive to exhibit catecholase activity. On the other hand, in methanol, it catalyzes not only the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) but also tetrachlorocatechol (TCC), a catechol which is very difficult to oxidize, under aerobic conditions. UV vis spectroscopic investigation shows that TCC oxidation proceeds through the formation of an intermediate. The intermediate has been characterized by an electron spray ionizaton-mass spectrometry study, which suggests a bidentate rather than a monodentate mode of TCC coordination in that intermediate, and this proposition have been verified by density functional theory calculation. The complex also exhibits phosphatase (with substrate p-nitrophenylphosphate) and DNA cleavage activities. The DNA cleavage activity exhibited by complex 1 most probably proceeds through a hydroxyl radical pathway. The bioactivity study suggests the possible applications of complex 1 as a site specific recognition of DNA and/or as an anticancer agent.

Correlation of structural disorder with the reversible discharge capacity of nickel hydroxide electrode

Hydrothermal treatment of a slurry of badly crystalline (beta(bc)) nickel hydroxide at different temperatures (65-170 degrees C) results in the progressive ordering of the structure by the step-wise elimination of disorders. Interstratification is eliminated at 140 degrees C, while cation vacancies are eliminated at 170 degrees C. A small percentage of stacking faults continue to persist even in `crystalline' samples. Electrochemical investigations show that the crystalline nickel hydroxide has a very low (0.4 e/Ni) reversible charge storage capacity. An incidence of at least 15% stacking faults combined with cation vacancies is essential for nickel hydroxide to perform close to its theoretical (1 e/ Ni) discharge capacity. (c) 2005 The Electrochemical Society.

Extraordinary high strain rate superplasticity in electrodeposited nano-nickel and alloys

Superplastic materials exhibit very large elongations to failure,typically >500%, and this enables commercial forming of complex shaped components at slow strain rates of similar to 10(-4) s(-1). We report extraordinary record superplastic elongations to failure of up to 5300% at both high strain rates and low temperature in electrodeposited nanocrystalline Ni and some Ni alloys. Superplasticity is not related to the presence of sulfur or a low melting phase at grain boundaries. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Potentiometric and spectrophotometric investigation of nickel-monoethanol-amine complexes

A detailed study of nickel-monoethanolamine complexes has been made employing potentiometric and spectrophotometric methods. The conditions for the formation of mono as well as polynuclear complexes have been investigated by potentiometric method. Evidence is presented for the formation of the following complexes and their stability constants are determined: NiA2+, Ni22+, Ni32+, NiA42+, NiA52+, NiA22+, Ni2A24+ and Ni3A36+. Combining potentiometric data with the spectrophotometric data, absorption spectra of the pure mononuclear complexes NiA2+ to NiA42+ and NiA2+6 have been computed. The absorption spectrum of NiA2+6 has been discussed on the basis of ligand field and molecular orbital theories. The absorption spectra of intermediate complexes have been interpreted on the basis of average ligand field theory. There has been good agreement between the experimental (10,400 cm-1) value of 10 Dq of NiA2+6 and the calculated value of 10 Dq (11,400 cm-1) on the basis of M.O. theory.

Nitrosation of N,N′-ethylenebis-(acetylacetoneimine) complexes of copper (II) and nickel(II) and characterization of the products

Isonitroso derivatives of copper(II) and nickel(II) complexes of N,N′-ethylenebis(acetylacetoneimine) have been prepared by nitrosation of the respective complexes using nitric oxide as well as nitrite ion. The condensation of isonitrosoacetylacetone in the presence and in the absence of nickel(II) has been investigated. The i.r. and electronic spectra and magnetic moment of the nickel(II) and copper(II) complexes have been studied. The nature of bonding of the ligand to the metal ion is discussed. The complexes have planar structures.

Studies on the hydrolysis of metal ions - Part II-Nickel

A detailed investigation of the hydrolysis of nickel in the lower concentration range has been made. The results have been analysed on the basis of 'Core + links' theory and on the assumption of the formation of one predominant complex. Evidence is obtained for the formation of Ni2 (OH)62- and its stability constant is calculated to be 1038.78

Nickel(II) complexes of 1-benzyl-2-phenylbenzimidazole

Nickel(II) complexes of 1-benzyl-2-phenylbenzimidazole (BPBI) of the general formula [Ni(BPBI)2X2](X=Cl-, Br-, NCS- or NO3-) have been prepared and their magnetic moments, i.r. and electronic spectra studied. [Ni(BPBI)2Cl2] has a pseudotetrahedral structure while [Ni(BPBI)2 Br2] exists as square planar and speudotetrahedral isomers. [Ni(BPBI)2I2] and [NI(BPBI)2(NCS)2] have square planar stereochemistry. The nitrato complex [Ni(BPBI)2(NO)3)2] exists in two different octahedral modifications in the solid state.

Potentiometric and spectrophotometric investigations of nickel-triethanolamine complexes

A detailed study of nickel-triethanolamine complexes has been made employing potentiometric and spectrophotometric methods. The potentiometric method has been used to investigate the conditions for the formation of both mono- and polynuclear complexes. The formulae and the stability constants of the following complexes have been determined Ni(TEA)2+, Ni(TEA)22+, and Ni2(TEA)24+. Absorption spectra of pure mononuclear complexes have been computed by the combination of potentiometric and spectrophotometric methods. The results are discussed on the basis of ligand field theory. Comparison of the step constants of the nickel-ethanolamines (mono-, di- and tri-) shows a slight chelate effect in these complexes due to coordination through hydroxyl oxygen. In the case of polynuclear complexes it is likely that bridging occurs through hydroxyl oxygen.

Reactions of coordinated bivalent tetradentate schiff-base chelates of nickel (II) and palladium (II)

Reactions of N,N′-n-propylene-bis(acetylacetoneimino) metal (II), M[n-P-(AI)2], where M=Ni(II) or Pd(II), with nitrosating reagents have been investigated. Mono- and di-nitrosated complexes were obtained selectively, depending upon the concentration of the nitrosating reagents and the reaction time. In both the cases, the γ-CH group is transformed to an ambidentate isonitroso group (>C=NOH), which coordinates to the metal ion by dislodging the already coordinated carbonyl group. The factors influencing the mode of binding of the isonitroso group have been discussed. The bromination reactions of the mono-nitrosated products of M[n-P-(AI)2] and Pd (II) complexes, Pd [E/i-P-(AI)2], where E/i-P-(AI)2 is a dianion of ethylene/i-propylene-bis (acetylacetoneimine), are also reported. The reaction products have been characterized by elemental analyses, electrical conductivity molecular weight determination, and ir, pmr and electronic spectral data.

Isobaric electrical resistance along the critical line in nickel: An experimental test of universality

High-precision measurement of the electrical resistance of nickel along its critical line, a first attempt of this kind, as a function of pressure to 47.5 kbar is reported. Our analysis yields the values of the critical exponents α=α’=-0.115±0.005 and the amplitude ratios ‖A/A’‖=1.17±0.07 and ‖D/D’‖=1.2±0.1. These values are in close agreement with those predicted by renormalization-group (RG) theory. Moreover, this investigation provides an unambiguous experimental verification to one of the key consequences of RG theory that the critical exponents and amplitudes ratios are insensitive to pressure variation in nickel, a Heisenberg ferromagnet.

Evidence for holes on oxygen in some nickel oxides

Core-level spectroscopic studies show the presence of holes on oxygen in LaNiO3 and LiNiO2 Nickel in these oxides seems to be essentially in the 2+ state instead of the 3+ state-where it would formally be expected to be on the basis of the stoichiometry.