Synthesis and crystal structure characterization of iron(II), cobalt(II) and nickel(II) complexes with 1,3-bis(2-pyridylmethylthio)propane

Three new mononuclear complexes of nitrogen-sulfur donor sets, formulated as (Fe-II(L)Cl-2] (1), [Co-II(L)Cl-2] (2) and [Ni-II(L)Cl-2] (3) where L = 1,3-bis(2-pyridylmethylthio)propane, were synthesized and isolated in their pure form. All the complexes were characterized by physicochemical and spectroscopic methods. The solid state structures of complexes I and 3 have been established by single crystal X-ray crystallography. The structural analysis evidences isomorphous crystals with the metal ion in a distorted octahedral geometry that comprises NSSN ligand donors with trans located pyridine rings and chlorides in cis positions. In dimethylformamide solution, the complexes were found to exhibit Fe-II/Fe-III, co(II)/co(III) and Ni-II/Ni-III quasi-reversible redox couples in cyclic voltammograms with E-1/2 values (versus Ag/AgCl at 298 K) of +0.295, +0.795 and +0.745 V for 1, 2 and 3, respectively. (C) 2009 Elsevier Ltd. All rights reserved.

A new oxidation catalyst system using fluorous cobalt(II) species in water-supercritical carbon dioxide (C-H free environment)

Stabilized water droplet dispersed in supercritical carbon dioxide fluid is demonstrated to be an excellent alternative solvent system to acetic acid for air oxidation of a number of alkyl aromatic hydrocarbons using Co(II) species at mild conditions.

Isomeric olefin tetracarbonyl complexes of tungsten(I): an infrared spectroelectrochemical study at low temperatures

In situ electrolysis within an optically transparent thin-layer electrochemical (OTTLE) cell was applied at 293-243 K in combination with FTIR spectroscopy to monitor spectral changes in the carbonyl stretching region accompanying oxidation of four tetracarbonyl olefin complexes of tungsten(0), viz., trans-[W(CO)(4)(eta(2)-ethene)(2)], trans-[W(CO)(4)(eta(2)-norbornene)(2)], [W(CO)(4)(eta(4)-cycloocta-1,5-diene)], and [W(CO)(4)(eta(4)-norbornadiene)]. In all cases, the one-electron-oxidized radical cations (17-electron complexes) have been identified by their characteristic nu(CO) patterns. For the bidentate diene ligands, the cis stereochemistry is essentially fixed in both the 18- and 17-electron complexes. The radical cation of the trans-bis(ethene) complex was observed only at 243 K, while at room temperature it isomerized rapidly to the corresponding cis-isomer. The thermal stability of the three studied radical cations in the cis configuration correlates with the relative strength of the W-CO bonds in the positions trans to the olefin ligand, which are more affected by the oxidation than the axial W-CO bonds. For the bulky norbornene ligands, their trans configuration in the bis(norbornene) complex remains preserved after the oxidation in the whole temperature range studied. The limited thermal stability of the radical cations of the trans-bis(alkene) complexes is ascribed to dissociation of the alkene ligands. The spectroelectrochemical results are in very good agreement with data obtained earlier by DFT (B3LYP) calculations.

Cobalt(III) complexes of some aromatic thiohydrazides – Synthesis, characterization and structure

Co(NH3)(5)Cl]Cl-2 forms neutral 1:3 complex by reaction with aromatic thiohydrazides, i.e. thiobenzhydrazide, o-hydroxythiobenzhydrazide, thiophen-2-thiohydrazide and furan-2-thiohydrazide. All these complexes are diamagnetic and have been characterized by elemental analysis and combination of spectroscopic methods. Cyclic voltammometry of the complexes shows irreversible metal centered and ligand centered electron transfer reactions. One complex, tris-o-hydroxythiobenzhydrazidocobalt(III),has been crystallized from DMSO solution to produce solvated crystals and its structure has been established by X-ray crystallography. Cobalt(III) ion is linked through three hydrazinic nitrogen and three sulfur atoms of three identical deprotonated ligand molecules in a distorted octahedral environment. Involvement of -OH group in intramolecular and intermolecular hydrogen bonding is crucial for crystal formation.

Forecasting the future: an overview of the strategic planning of the Bournemouth and Poole conurbation

An important part of strategic planning’s purpose should be to attempt to forecast the future, not simply to belatedly respond to events, or accept the future as inevitable. This paper puts forward a conceptual approach for seeking to achieve these aims and uses the Bournemouth and Poole area in Dorset as a vehicle for applying the basic methodology. The area has been chosen because of the significant issues that it currently faces in planning terms; and its future development possibilities. In order that alternative future choices for the area – different ‘developmental trajectories’ – can be evaluated, they must be carefully and logically constructed. Four Futures for Bournemouth/Poole have been put forward; they are titled and colour-coded: Future One is Maximising Growth – Golden Prospect which seeks to achieve the highest level of economic prosperity of the area; Future Two is Incremental Growth – Solid Silver which attempts to facilitate a steady, continuing, controlled pattern of the development for the area; Future Three is Steady State – Cobalt Blue which suggests that people in the area could be more concerned with preserving their quality of life in terms of their leisure and recreation rather than increasing wealth; Future Four is Environment First – Jade Green which makes the area’s environmental protection its top priority even at the possible expense of economic prosperity. The scenarios proposed here are not sacrosanct. Nor are they simply confined to the Bournemouth and Poole area. In theory, suitably modified, they could use in a variety of different contexts. Consideration of the scenarios – wherever located - might then generate other, additional scenarios. These are called hybrids, alloys and amalgams. Likewise it might identify some of them as inappropriate or impossible. Most likely, careful consideration of the scenarios will suggest hybrid scenarios, in which features from different scenarios are combined to produce alternative or additional futures for consideration. The real issue then becomes how best to fashion such a future for the particular area under consideration

Configurational preferences of two 1,2-diamine adducts of bis(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)cobalt(II)

The preparation, the IR and ligand field spectra and the structures of the mixed-ligand addition compounds [(N,N-dimethyl-1,2-diaminoethane)bis(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)cobalt(II)], [Co(thtf)2me2en], and [(N,N,N′,N′-tetramethyl-1,2-diaminoethane)bis(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)cobalt(II)], [Co(thtf)2me4en], are reported. The structures were determined by single crystal X-ray diffraction analysis (monoclinic, space group P21/c, Z=4 with a=10.708(6), b=19.531(6), c=13.352(6) Å, β=111.64(10)°, R1=0.0642 and wR2=0.1719 for [Co(thtf)2(me2en)] and a=12.033(6), b=15.565(6), c=15.339(6) Å, β=92.57(6)°, R1=0.0612 and wR2=0.1504 for [Co(thtf)2me4en]). The structures are distorted octahedral and the shortest cobalt–cobalt separation distances are 5.388(2) Å in [Co(thtf)2me2en] and 8.675(3) Å in [Co(thtf)2me4en]. In both compounds the diamine molecules attain the gauche conformation. The U(Z,Z) conformation of the β-dione leads to a semi-chair conformation of the β-dionato chelate rings. The relative orientation of the groups attached to the β-dionato moiety depends on the extent of stereoelectronic effects the N-substitution of the diamine entails. In [Co(thtf)2me2en] the intraligand distance separating the trifluoromethyl carbon atoms is 5.281(18) Å while in [Co(thtf)2me2en] it increases to 8.338(9) Å. The cobalt–cobalt separation distance, the orientation of the chelate rings and the extent of N-substitution seem to affect hydrogen bonding. While in [Co(thtf)2me2en] inter- and intraligand hydrogen bonding is implicated, it is totally absent in [Co(thtf)2me4en].

Reaction of (±)-1,1′-binaphthyl-2,2′-diyl hydrogen phosphate {(±)-phosH} with copper(II), cobalt(II) and iron(II) compounds; Identification by x-ray diffraction of [Co(CH3OH)4(H2O)2][(+)-phos][(−)-phos]. 2CH3OH·H2O

[Cu2(μO2CCH3)4(H2O)2], [CuCO3·Cu(OH)2], [CoSO4·7H2O], [Co((+)-tartrate)], and [FeSO4·7H2O] react with excess racemic (±)- 1,1′-binaphthyl-2,2′-diyl hydrogen phosphate {(±)-PhosH} to give mononuclear CuII, CoII and FeII products. The cobalt product, [Co(CH3OH)4(H2O)2]((+)-Phos)((−)-Phos) ·2CH3OH·H2O (7), has been identified by X-ray diffraction. The high-spin, octahedral CoII atom is ligated by four equatorial methanol molecules and two axial water molecules. A (+)- and a (−)-Phos− ion are associated with each molecule of the complex but are not coordinated to the metal centre. For the other CoII, CuII and FeII samples of similar formulation to (7) it is also thought that the Phos− ions are not bonded directly to the metal. When some of the CuII and CoII samples are heated under high vacuum there is evidence that the Phos− ions are coordinated directly to the metals in the products.

1,1′-Bis(diphenylphosphino)ferrocene bridging two mono(cyclopentadienyl) cobalt moieties: synthesis, structure, electrochemistry and DFT studies

Reaction of [Co(eta(5)-C5H5)(CO)(2)], 1, with 1,1'-bis(diphenylphosphino)ferrocene (dppf) yields the new trinuclear complex [Co(eta(5)-C5H5)(CO)](2)(mu-dppf), 2, which was structurally characterised by single crystal X-ray diffraction and showed two Co(eta(5)-C5H5)(CO) moieties covalently linked by a dppf bridge. Electrochemical studies in dichloromethane revealed that both Co(I) and Fe(II) in the precursors were oxidized to Co(II)/Co(III) and Fe(III), respectively. On the other hand, in 2 the two first oxidation waves were assigned to Co, the Fe(II) centre requiring a higher potential than in free dppf. DFT calculations showed that the HOMOs of 2 were localised in the Co fragments, owing to the destabilisation of the Co(eta(5)-C5H5)(CO) orbitals after binding dppf.

Synthesis and spectroscopic properties of cobalt(III) complexes of some aroyl hydrazones: x-ray crystal structures of one cobalt(III) complex and two aroyl hydrazone ligands

Cobalt(III) complexes of diacetyl monooxime benzoyl hydrazone (dmoBH(2)) and diacetyl monooxime isonicotinoyl hydrazone (dmoInH(2)) have been synthesized and characterized by elemental analyses and spectroscopic methods. The X-ray crystal structures of the two hydrazone ligands, as well as that of the cobalt(III) complex [Co(III)(dmoInH)(2)]Cl center dot 2H(2)O, are also reported. It is found that in the cobalt(III) complexes the Co(III) ion is hexa-coordinated, the hydrazone ligands behaving as mono-anionic tridentate O,N,N donors. In the [Co(III)(dmoInH) (2)]Cl center dot 2H(2)O complex, the amide and the oxime hydrogens are deprotonated for both the ligands, while the isonicotine nitrogens are protonated. In the [Co(III)(d-moBH)(2)] Cl complex, only the amide nitrogens are deprotonated. It is shown that the additional hydrogen bonding capability of the isonicotine nitrogen results in different conformation and supramolecular structure for dmoInH(2), compared to dmoBH(2), in the solid state. Comparing the structure of the [CoIII(dmoInH)(2)]Cl center dot 2H(2)O with that of the Zn(II) complex of the same ligand, reported earlier, it is seen that the metal ion has a profound influence on the supramolecular structure, due to change in geometrical dispositions of the chelate rings.

Preparation and magnetic properties of barium ferrites substituted with manganese, cobalt, and tin

Barium ferrites substituted by Mn–Sn, Co–Sn, and Mn–Co–Sn with general formulae BaFe12−2xMnxSnxO19 (x=0.2–1.0), BaFe12−2xCoxSnxO19 (x=0.2–0.8), and BaFe12−2xCox/2Mnx/2SnxO19 (x=0.1–0.6), respectively, have been prepared by a previously reported co-precipitation method. The efficiency of the method was refined by lowering the reaction temperature and shortening the required reaction time, due to which crystallinity improved and the value of saturated magnetization increased as well. Low coercivity temperature coefficients, which are adjustable by doping, were achieved by Mn–Sn and Mn–Co–Sn doping. Synthesis efficiency and the effect of doping are discussed taking into account accumulated data concerning the synthesis and crystal structure of ferrites.

Cobalt incorporation in calcite: Thermochemistry of (Ca,Co)CO3 solid solutions from density functional theory simulations

The incorporation of cobalt in mixed metal carbonates is a possible route to the immobilization of this toxic element in the environment. However, the thermodynamics of (Ca,Co)CO3 solid solutions are still unclear due to conflicting data from experiment and from the observation of natural ocurrences. We report here the results of a computer simulation study of the mixing of calcite (CaCO3) and spherocobaltite (CoCO3), using density functional theory calculations. Our simulations suggest that previously proposed thermodynamic models, based only on the range of observed compositions, significantly overestimate the solubility between the two solids and therefore underestimate the extension of the miscibility gap under ambient conditions. The enthalpy of mixing of the disordered solid solution is strongly positive and moderately asymmetric: calcium incorporation in spherocobaltite is more endothermic than cobalt incorporation in calcite. Ordering of the impurities in (0001) layers is energetically favourable with respect to the disordered solid solution at low temperatures and intermediate compositions, but the ordered phase is still unstable to demixing. We calculate the solvus and spinodal lines in the phase diagram using a sub-regular solution model, and conclude that many Ca1-xCoxCO3 mineral solid solutions (with observed compositions of up to x=0.027, and above x=0.93) are metastable with respect to phase separation. We also calculate solid/aqueous distribution coefficients to evaluate the effect of the strong non-ideality of mixing on the equilibrium with aqueous solution, showing that the thermodynamically-driven incorporation of cobalt in calcite (and of calcium in spherocobaltite) is always very low, regardless of the Co/Ca ratio of the aqueous environment.

The interplay of metal-atom ordering, Fermi leveltuning and thermoelectric properties in cobalt shandites Co3M2S2 (M = Sn, In)

A combination of structural, physical and computational techniques including powder X-ray and neutron diffraction, SQUID magnetometry, electrical and thermal transport measurements, DFT calculations and 119Sn Mössbauer and X-ray photoelec-tron spectroscopies has been applied to Co3Sn2-xInxS2 (0 ≤ x ≤ 2) in an effort to understand the relationship between metal-atom ordering and physical properties as the Fermi level is systematically varied. Whilst solid solution behavior is found throughout the composition region, powder neutron diffraction reveals that indium preferentially occupies an inter-layer site over an alternative kagome-like intra-layer site. DFT calculations indicate that this ordering, which leads to a lowering of energy, is related to the dif-fering bonding properties of tin and indium. Spectroscopic data suggest that throughout the composition range 0 ≤ x ≤ 2, all ele-ments adopt oxidation states that are significantly reduced from expectations based on formal charges. Chemical substitution ena-bles the electrical transport properties to be controlled through tuning of the Fermi level within a region of the density of states, which comprises narrow bands of predominantly Co d-character. This leads to a compositionally-induced double metal-to-semiconductor-to-metal transition. The marked increase in the Seebeck coefficient as the semiconducting region is approached leads to a substantial improvement in the thermoelectric figure of merit, ZT, which exhibits a maximum of ZT = 0.32 at 673 K. At 425 K, the figure of merit for phases in the region 0.8 ≤ x ≤ 0.85 is amongst the highest reported for sulphide phases, suggesting these materials may have applications in low-grade waste heat recovery.

The impact of charge transfer and structural disorder on the thermoelectric properties of cobalt intercalated TiS2

A family of phases, CoxTiS2 (0 ≤ x ≤ 0.75) has been prepared and characterised by powder X-ray and neutron diffraction, electrical and thermal transport property measurements, thermal analysis and SQUID magnetometry. With increasing cobalt content, the structure evolves from a disordered arrangement of cobalt ions in octahedral sites located in the van der Waals’ gap (x ≤ 0.2), through three different ordered vacancy phases, to a second disordered phase at x ≥ 0.67. Powder neutron diffraction reveals that both octahedral and tetrahedral inter-layer sites are occupied in Co0.67TiS2. Charge transfer from the cobalt guest to the TiS2 host affords a systematic tuning of the electrical and thermal transport properties. At low levels of cobalt intercalation (x < 0.1), the charge transfer increases the electrical conductivity sufficiently to offset the concomitant reduction in |S|. This, together with a reduction in the overall thermal conductivity leads to thermoelectric figures of merit that are 25 % higher than that of TiS2, ZT reaching 0.30 at 573 K for CoxTiS2 with 0.04 ≤ x ≤ 0.08. Whilst the electrical conductivity is further increased at higher cobalt contents, the reduction in |S| is more marked due to the higher charge carrier concentration. Furthermore both the charge carrier and lattice contributions to the thermal conductivity are increased in the electrically conductive ordered-vacancy phases, with the result that the thermoelectric performance is significantly degraded. These results illustrate the competition between the effects of charge transfer from guest to host and the disorder generated when cobalt cations are incorporated in the inter-layer space.

Correlation between vertical misfits and stresses transmitted to implants from metal frameworks

An inappropriate prosthetic fit could cause stress over the interface implant/bone. The objective of this study was to compare stresses transmitted to implants from frameworks cast using different materials and to investigate a possible correlation between vertical misfits and these stresses. Fifteen one-piece cast frameworks simulating bars for fixed prosthesis in a model with five implants were fabricated and arranged into three different groups according to the material used for casting: CP Ti (commercially pure titanium), Co-Cr (cobalt-chromium) or Ni-Cr-Ti (nickel-chromium-titanium) alloys. Each framework was installed over the metal model with all screws tightened to a 10 N cm torque and then, vertical misfits were measured using an optical microscope. The stresses transmitted to implants were measured using quantitative photoelastic analysis in values of maximum shear stress (T), when each framework was tightened to the photoelastic model to a 10 N cm standardized torque. Stress data were statistically analyzed using one-way ANOVA and Tukey`s test and correlation tests were performed using Pearson`s rank correlation (alpha = 0.05). Mean and standard deviation values of vertical misfit are presented for CP Ti (22.40 +/- 9.05 mu m), Co-Cr (66.41 +/- 35.47 mu m) and Ni-Cr-Ti (32.20 +/- 24.47 mu m). Stresses generated by Co-Cr alloy (tau = 7.70 +/- 2.16 kPa) were significantly higher than those generated by CP Ti (tau = 5.86 +/- 1.55 kPa, p = 0.018) and Ni-Cr-Ti alloy (tau =5.74 +/- 3.05 kPa, p = 0.011), which were similar (p = 0.982). Correlations between vertical misfits and stresses around the implants were not significant as for any evaluated materials. (C) 2011 Elsevier Ltd. All rights reserved.

In vitro cytotoxicity of dental alloys and cpTi obtained by casting

Background: This study aimed to compare the cytotoxicity of base-metal dental alloys and to evaluate if the casting method could influence their cytotoxicity. Methods: Disks of base-metal dental alloys were cast by two methods: plasma, under argon atmosphere, injected by vacuum-pressure; and oxygen-gas flame, injected by centrifugation, except Ti-6Al-4V and commercially pure titanium (cpTi), cast only by plasma. SCC9 cells were cultured in culture media D-MEM/Ham`s F12 supplemented, at 37 degrees C in a humidified atmosphere of 5% carbon dioxide and 95% air, on the previously prepared disks. At subconfluence in wells without disks (control), cell number and viability were evaluated. Results: In plasma method, cpTi and Ti-6Al-4V were similar to control and presented higher number of cells than all other alloys, followed by Ni-Cr. In oxygen-gas name method, all alloys presented fewer cells than control. Ni-Cr presented more cells than any other alloy, followed by Co-Cr-Mo-W which presented more cells than Ni-Cr-Ti, Co-Cr-Mo, and Ni-Cr-Be. There were no significant differences between casting methods related to cell number. Cell viability was not affected by either chemical composition or casting methods. Conclusion: cpTi and Ti-6Al-4V were not cytotoxic while Ni-Cr-Be was the most cytotoxic among tested alloys. The casting method did not affect cytotoxicity of the alloys. (c) 2007 Wiley Periodicals, Inc.