The syntheses and characterization of nickel complexes; investigation of Ni(dppp)2 and [NiX(dppp)n]x, potentially catalytically active nickel(0)/(I) species for cross-coupling reactions

This thesis describes an investigation in which we compare Ni(0), Ni(I) and Ni(II) complexes containing 1,3-bis(diphenylphosphino)propane (dppp) as a phosphine ligand for their abilities to effect three types of cross-coupling reactions: Buchwald-Hartwig Amination, Heck-Mizoroki, and Suzuki-Miyaura cross-coupling reactions with different types of substrates. The Ni(0) complex Ni(dppp)2 is known and we have synthesized it via a new procedure involving zinc reduction of the known NiCl2(dppp) in the presence of an excess of dppp. The Ni(0) complex was characterized by NMR spectroscopy and X-ray crystallography. Since Ni(I) complexes of dppp seem unknown, we have synthesized what at this stage appear to be NiXdpppn/[NiX(dppp)n]x (X = Cl, Br, I; n = 1,2, x = 1, 2) by comproportionation of molar equivalents of Ni(dppp)2 and NiX2dppp, X= Cl, Br, I.

The syntheses and characterization of nickel complexes; investigation of Ni(dppp)2 and [NiX(dppp)n]x, potentially catalytically active nickel(0)/(I) species for cross-coupling reactions

This thesis describes an investigation in which we compare Ni(0), Ni(I) and Ni(II) complexes containing 1,3-bis(diphenylphosphino)propane (dppp) as a phosphine ligand for their abilities to effect three types of cross-coupling reactions: Buchwald-Hartwig Amination, Heck-Mizoroki, and Suzuki-Miyaura cross-coupling reactions with different types of substrates. The Ni(0) complex Ni(dppp)2 is known and we have synthesized it via a new procedure involving zinc reduction of the known NiCl2(dppp) in the presence of an excess of dppp. The Ni(0) complex was characterized by NMR spectroscopy and X-ray crystallography. Since Ni(I) complexes of dppp seem unknown, we have synthesized what at this stage appear to be NiXdpppn/[NiX(dppp)n]x (X = Cl, Br, I; n = 1,2, x = 1, 2) by comproportionation of molar equivalents of Ni(dppp)2 and NiX2dppp, X= Cl, Br, I.

Observation of two-magnon bound states in the spin-1 anisotropic Heisenberg antiferromagnetic chain system NiCl2-4SC(NH2)(2)

Results of systematic tunable-frequency ESR studies of the spin dynamics in NiCl2-4SC(NH2)(2) (known as DTN), a gapped S = 1 chain system with easy-plane anisotropy dominating over the exchange coupling (large-D chain), are presented. We have obtained direct evidence for two-magnon bound states, predicted for S = 1 large-D spin chains in the fully spin-polarized (FSP) phase. The frequency-field dependence of the corresponding excitations was calculated using the set of parameters obtained earlier [S.A. Zvyagin, et al., Phys. Rev. Lett. 98 (2007) 047205]. Very good agreement between the calculations and the experiment was obtained. It is argued that the observation of transitions from the ground to two-magnon bound states might indicate a more complex picture of magnetic interactions in DTN, involving a finite in-plane anisotropy. (C) 2007 Elsevier B.V. All rights reserved.

Synthesis, characterization and cytotoxic activities of the [RuCl(2)(NO)(dppp)(L)]PF(6) complexes

The synthesis and characterization of ruthenium compounds of the type [RuCl(2)(NO)(dppp)(L)]PF(6) [dppp = 1,3-bis(diphenylphosphino)propane; L = pyridine, 4-methylpyridine, 4-phenylpyridine and dimethyl sulfoxide] are described. The complexes were characterized by elemental analysis, UV/Vis and infrared spectroscopy, cyclic voltammetry, and X-ray crystallography for the complexes with the pyridine and 4-methylpyridine ligands. In vitro evaluation of these nitrosyl complexes revealed cytotoxic activity from 7.1 to 19.0 mu M against the MDA-MB-231 breast tumor cells and showed that, in this case, they are more active than the reference metallodrug cisplatin. The 1,3-bis(diphenylphosphino)propane and the N-heterocyclic ligands alone failed to show cytotoxic activities at the concentrations tested (maximum concentration utilized = 200 mu M). (C) 2009 Elsevier Inc. All rights reserved.

Structure and antimycobacterial activity of the novel organometallic [Pd(C-bzan)(SCN)(dppp)] compound

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Pancreas damage and intratracheal NiCl2 administration. Effects of nickel chloride.

Changes in activities of Cu-Zn superoxide dismutase (SOD- E.C.1.15.1.1.) and lactate dehydrogenase (LDH- E.C.1.1.1.27.) and levels of copper, total protein, triglycerides, phospholipids and total lipids were investigated in pancreas of rats after intratracheal administration of NiCl2 (8.4 mumol/kg). Nickel chloride induced increased SOD activity in pancreas and erythrocytes. This elevation was related to increased copper and decreased phospholipid content in pancreas of these animals. In conclusion, the ability of an animal to tolerate nickel chloride induced damage was governed by a delicate balance between the generation of cytotoxic agents and the various pancreas defense capabilities.

Structure and antimycobacterial activity of the novel organometallic [Pd(C-bzan)(SCN)(dppp)] compound

The organometallic compound [Pd(C-bzan)(SCN)(dppp)] {bzan = N-benzylideneaniline, dppp = 1,3-bis(diphenylphosphino)propane} was synthesized and characterized by elemental analyses, infrared and H-1 and P-31(H-1) NMR spectroscopies. The crystal and molecular structures of the title complex were determined by single-crystal X-ray diffraction techniques. In vitro antimycobacterial evaluation demonstrated that the compound [Pd(C-bzan)(SCN)(dppp)] displayed a MIC of 5.15 mu M, which is superior than those values found for some commonly used anti-TB drugs and other Pd(II) complexes. (C) 2012 Elsevier B.V. All rights reserved.

Bose-Einstein Condensation of Magnons in NiCl2-4SC(NH2)(2)

A Bose-Einstein condensation (BEC) has been observed in magnetic insulators in the last decade. The condensed bosons are magnons associated with an ordered magnetic phase induced by a magnetic field. We review the experiments in the spin-gap compound NiCl2-4SC(NH2)(2), in which the formation of BEC occurs by applying a magnetic field at low temperatures. This is a contribution to the celebration of the 50th anniversary of the Solid State and Low Temperature Laboratory of the University of So Paulo, where this compound was first magnetically characterized.

Low-temperature thermodynamic properties near the field-induced quantum critical point in NiCl2-4SC(NH2)(2)

We present a comprehensive experimental and theoretical investigation of the thermodynamic properties: specific heat, magnetization, and thermal expansion in the vicinity of the field-induced quantum critical point (QCP) around the lower critical field H-c1 approximate to 2 T in NiCl2-4SC(NH2)(2). A T-3/2 behavior in the specific heat and magnetization is observed at very low temperatures at H = H-c1, which is consistent with the universality class of Bose-Einstein condensation of magnons. The temperature dependence of the thermal expansion coefficient at H-c1 shows minor deviations from the expected T-1/2 behavior. Our experimental study is complemented by analytical calculations and quantum Monte Carlo simulations, which reproduce nicely the measured quantities. We analyze the thermal and the magnetic Gruneisen parameters, which are ideal quantities to identify QCPs. Both parameters diverge at H-c1 with the expected T-1 power law. By using the Ehrenfest relations at the second-order phase transition, we are able to estimate the pressure dependencies of the characteristic temperature and field scales.

Magnetic excitations in the spin-1 anisotropic antiferromagnet NiCl2-4SC(NH2)(2)

The spin-1 anisotropic antiferromagnet NiCl2-4SC(NH2)(2) exhibits a field-induced quantum phase transition that is formally analogous to Bose-Einstein condensation. Here we present results of systematic high-field electron spin resonance (ESR) experimental and theoretical studies of this compound with a special emphasis on single-ion two-magnon bound states. In order to clarify some remaining discrepancies between theory and experiment, the frequency-field dependence of magnetic excitations in this material is reanalyzed. In particular, a more comprehensive interpretation of the experimental signature of single-ion two-magnon bound states is shown to be fully consistent with theoretical results. We also clarify the structure of the ESR spectrum in the so-called intermediate phase.

Structure, magnetism and colour in simple bis­(phosphine)nickel(II) dihalide complexes : an experimental and theoretical investigation

The complex [1,2-bis­(di-tert-butyl­phosphan­yl)ethane-[kappa]2P,P']di­iodido­nickel(II), [NiI2(C18H40P2] or (dtbpe-[kappa]2P)NiI2, [dtbpe is 1,2-bis­(di-tert-butyl­phosphan­yl)ethane], is bright blue-green in the solid state and in solution, but, contrary to the structure predicted for a blue or green nickel(II) bis­(phos­phine) complex, it is found to be close to square planar in the solid state. The solution structure is deduced to be similar, because the optical spectra measured in solution and in the solid state contain similar absorptions. In solution at room temperature, no 31P{1H} NMR resonance is observed, but the very small solid-state magnetic moment at temperatures down to 4 K indicates that the weak paramagnetism of this nickel(II) complex can be ascribed to temperature independent paramagnetism, and that the complex has no unpaired electrons. The red [1,2-bis­(di-tert-butyl­phosphan­yl)ethane-[kappa]2P,P']di­chlorido­nickel(II), [NiCl2(C18H40P2] or (dtbpe-[kappa]2P)NiCl2, is very close to square planar and very weakly paramagnetic in the solid state and in solution, while the maroon [1,2-bis­(di-tert-butyl­phosphan­yl)ethane-[kappa]2P,P']di­bromido­nickel(II), [NiBr2(C18H40P2] or (dtbpe-[kappa]2P)NiBr2, is isostructural with the diiodide in the solid state, and displays paramagnetism inter­mediate between that of the dichloride and the diiodide in the solid state and in solution. Density functional calculations demonstrate that distortion from an ideal square plane for these complexes occurs on a flat potential energy surface. The calculations reproduce the observed structures and colours, and explain the trends observed for these and similar complexes. Although theoretical investigation identified magnetic-dipole-allowed excitations that are characteristic for temperature-independent paramagnetism (TIP), theory predicts the mol­ecules to be diamagnetic.

Use of 2-pyrimidineamidoxime to generate polynuclear homo-/heterometallic assemblies: synthesis, crystal structures and magnetic study with theoretical investigations on the exchange mechanism

Three new transition metal complexes using 2-pyrimidineamidoxime (pmadH(2)) as multidentate chelating and/or bridging ligand have been synthesized and characterized. The ligand pmadH(2) has two potential bridging functional groups mu-O and mu-(N-O)] and consequently shows several coordination modes. While a polymeric 1D Cu-II complex Cu(pmadH(2))(2)(NO3)](NO3) (1) was obtained upon treatment of Cu(NO3)(2)center dot 3H(2)O with pmadH(2) at room temperature in the absence of base, a high temperature reaction in the presence of base yielded a tetranuclear Cu-II-complex Cu-4(pmad)(2)(pmadH)(2)(NO3)](NO3)(H2O) (2). One of the Cu-II centers is in a square pyramidal environment while the other three are in a square planar geometry. Reaction of the same ligand with an equimolar mixture of both Cu(NO3)(2)center dot 3H(2)O and NiCl2 center dot 6H(2)O yielded a tetranuclear heterometallic (Cu2Ni2II)-Ni-II complex Cu2Ni2(pmad)(2)(pmadH)(2)Cl-2]center dot H2O (3) containing both square planar (Ni-II) and square pyramidal (Cu-II) metal centers. Complexes 1-3 represent the first examples of polynuclear metal complexes of 2-pyrimidineamidoxime. The analysis of variable temperature magnetic susceptibility data of 2 reveals that both ferromagnetic and antiferromagnetic interactions exist in this complex (J(1) = +10.7 cm(-1) and J(2) = -2.7 cm(-1) with g = 2.1) leading to a resultant ferromagnetic behavior. Complex 3 shows expected antiferromagnetic interaction between two Cu-II centers through -N-O- bridging pathway with J(1) = -3.4 cm(-1) and g = 2.08. DFT calculations have been used to corroborate the magnetic results.

Synthesis, X-ray crystal structure, DNA binding, antioxidant and cytotoxicity studies of Ni(II) and Pd(II) thiosemicarbazone complexes

New complexes, [Ni(HL)(PPh3)]Cl (1), [Pd(L)(PPh3)](2), and [Pd(L)(AsPh3)](3), were synthesized from the reactions of 4-chloro-5-methyl-salicylaldehyde thiosemicarbazone [H2L] with [NiCl2(PPh3)(2)], [PdCl2(PPh3)(2)] and [PdCl2(AsPh3)(2)]. They were characterized by IR, electronic, H-1-NMR spectral data. Further, the structures of the complexes have been determined by single crystal X-ray diffraction. While the thiosemicarbazone coordinated as binegative tridentate (ONS) in complexes 2 and 3, it is coordinated as mono negative tridentate (ONS) in 1. The interactions of the new complexes with calf thymus DNA was examined by absorption and emission spectra, and viscosity measurements. Moreover, the antioxidant properties of the new complexes have also been tested against DPPH radical in which complex 1 exhibited better activity than that of the other two complexes 2 and 3. The in vitro cytotoxicity of complexes 1-3 against A549 and HepG2 cell lines was assayed, and the new complexes exhibited higher cytotoxic activity with lower IC50 values indicating their efficiency in killing the cancer cells even at very low concentrations.

Synthesis of carbon nanotube bundles with mesoporous structure by a self-assembly solvothermal route

A kind of carbon nanotube bundle has been synthesized by a simple one-step solvothermal reaction between Na and hexachlorobenzene (HCB) using NiCl2 as catalyst precursor. Before the reaction, NiCl2 was initially dispersed ultrasonically in cyclohexane then prereduced by Na at 230degreesC to produce small Ni particles in reduced state. The tubes thus-produced have a uniform outer diameter of about 20 nm, an inner diameter of 4 nm, and are highly ordered assembled as bundles which have a 2D hexagonal arrangement as proven by SAXS and TEM experiments.

Synthesis and characterization of phenylene-thiophene all-conjugated diblock copolymers

Grignard metathesis (GRIM) polymerization for all-conjugated diblock copolymers comprising poly (2,5-dihexyloxy-1,4-phenylene) (PPP) and poly(3-hexylthiophene) (P3HT) blocks were systematically studied with LiCl as additive and 1,2-bis (diphenylphosphino) ethane nickel dichloride (Ni(dppe)Cl-2) or 1,3-bis(diphenylphosphino) propane nickel dichloride (Ni(dppp)Cl-2) as catalyst. It was found that the addition order of the monomers was crucial for the success of copolymerization. With the monomer addition in the order of phenyl and then thienyl Grignard reagents, all-conjugated PPP-b-P3HT diblock copolymers with different block ratios were successfully synthesized. In contrast, the inverted addition order only afforded a mixture containing both block copolymers and deactivated or end-capped homopolymers.