Synthesis, characterization and molecular structure of 1,1′ bis (diphenyl phosphino ferrocene) dioxide complex of the cis-uranyl dichloride

A 1,1' bis(diphenyl phosphino ferrocene) dioxide complex of the uranyl dichloride was synthesized and characterized by elemental analysis, H-1, P-31{H-1} NMR and X-ray diffraction methods. The structure of the compound shows that the uranium(VI) ion is surrounded by four oxygen and two chlorine atoms in an octahedral geometry. Two oxygen atoms from the bis (diphenyl phosphino ferrocene) dioxide and two chlorine atoms form a square planar arrangement. Two uranyl oxygen atoms occupy the axial positions. The bis(diphenyl phosphino ferrocene) dioxide ligand acts as a bidentate chelating ligand with a bite angle of 82.90(16)degrees around the uranyl group. The two chlorine atoms are mutually cis with a CI-U-Cl angle of 97.75(7)degrees.

Complexes of NiX2 (X=Cl− and NO3−) with a NNO donor Schiff base: anion dependent structural variations and spectroscopic behaviour

Two new nickel(11) complexes, [NiLL'(H2O)(2)Cl] (1) and [{NiLL'(H2O)](2)(mu-H)]NO3·H2O(2), have been synthesized using a tridentate Schiff base ligand, HL, 2-[(2-dimethylamino-ethylimino)-methyl]-phenol, along with Cl- or NO3(-) as an anionic co-ligand or counter anion (where L'H = salicylaldehyde). Both complexes have been characterized by X-ray crystallography. The structural analyses reveal that complex 1 is mononuclear whereas 2 is a hydrogen-bridged dinuclear complex. The Ni(II) ions possess a distorted octahedral geometry in both structures. Both complexes show negative solvatochromic behaviour with increasing donor number (DN) of the solvent. In more coordinating solvents, like DMSO or methanol, the colour of the solutions is green, whereas in less coordinating solvents, like dichloromethane (DCM) or acetonitrile, it is red.

Synthesis, crystal structure, and magnetic properties of a very rare double μ-1,1-azido- and a μ-1,1-(OMe)-bridged FeIII dimer containing a N,N,O-donor tridentate Schiff base ligand

Two new Fe-III complexes, [Fe2L2(mu-OMe)(2)(NCS)(2)] (1) and [Fe2L2(mu-N-3)(2)(N-3)(2)] (2), have been synthesized using a N,N,O-donor tridentate Schiff base ligand HL {2-[(2-dimethylaminoethylimino)methyl]phenol}, the condensation product of salicylaldehyde and N,N-dimethyl-1,2-diaminoethane. The complexes were characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. Both crystal structures are centrosymmetric dimers containing two Fe-III atoms, which are bridged in compound 1 by two methoxy anions and in compound 2 by two mu-1,1-azides. The chelating tridentate Schiff base and a terminal thiocyanato (for 1) or azido (for 2) group complete the hexacoordination of the distorted octahedral environment of each iron center. The magnetic properties of compound 1 show the presence of antiferromagnetic exchange interactions mediated by double methoxy bridges (J = -29.45 cm(-1)). Compound 2 shows the presence of very weak ferromagnetic exchange interactions mediated by double mu-1,1-N-3 bridges (J = 1.08 cm(-1)).

Epoxide ring opening in a zinc(II) complex in water without any Lewis acid catalyst: formation of only one diastereomer out of 2

The epoxide ring in 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (L) opens up in its reaction with 4-methylaniline and 4-methoxyaniline in water in equimolar proportion at room temperature without any Lewis acid catalyst to give a monohydrate of 6-(4-methyl-phenylamino)-5,6-dihydro-1,10-phenanthrolin-5-ol (L′·H2O) and 6-(4-methoxyphenyl-amino)-5,6-dihydro-1,10-phenanthrolin-5-ol (L″) respectively. Reaction time decreases from 72 to 14 h in boiling water. But the yields become less. Reaction of L with Zn(ClO4)2·6H2O in methanol in 3:1 molar ratio at room temperature affords white [ZnL3](ClO4)2·H2O. The X-ray crystal structure of the acetonitrile solvate [ZnL3](ClO4)2·MeCN has been determined which shows that the metal has a distorted octahedral N6 coordination sphere. [ZnL3](ClO4)2·2H2O reacts with 4-methylaniline and 4-methoxyaniline in boiling water in 1:3 molar proportion in the absence of any Lewis acid catalyst to produce [ZnL′3](ClO4)2·4H2O and [ZnL″3](ClO4)2·H2O, respectively in 1–4 h time in somewhat low yield. In the 1H NMR spectra of [ZnL′3](ClO4)2·4H2O and [ZnL″3](ClO4)2·H2O, only one sharp methyl signal is observed implicating that only one diastereomer out of the 23 possibilities is formed. The same diastereomers are obtained when L′·H2O and L″ are reacted directly with Zn(ClO4)2·6H2O in tetrahydrofuran at room temperature in very good yields. Reactions of L′·H2O and L″ with Ru(phen)2Cl2·2H2O (phen = 1,10-phenanthroline) in equimolar proportion in methanol–water mixture under refluxing condition lead to the isolation of two diastereomers of [Ru(phen)2L′](ClO4)2·2H2O and [Ru(phen)2L″](ClO4)2·2H2O.

Trinuclear and tetranuclear adduct formation between sodium perchlorate and copper(II) complexes of salicylaldimine type ligands: structural characterization and theoretical investigation

The synthesis of two new sodium perchlorate adducts (1:2 and 1:3) with copper(II) "ligand-complexes'' is reported. One adduct is trinuclear [(CuL(1))(2)NaClO(4)] (1) and the other is tetranuclear [(CuL(2))(3)Na]ClO(4)center dot EtOH (2). The ligands are the tetradentate di-Schiff base of 1,3-propanediamines and salicylaldehyde (H(2)L(1)) or 2-hydroxyacetophenone (H(2)L(2)). Both complexes have been characterized by X-ray single crystal structure analyses. In both structures, the sodium cation has a six-coordinate distorted octahedral environment being bonded to four oxygen atoms from two Schiff-base complexes in addition to a chelated perchlorate anion in 1 and to six oxygen atoms from three Schiff-base complexes in 2. We have carried out a DFT theoretical study (RI-B97-D/def2-SVP level of theory) to compute and compare the formation energies of 1:2 and 1:3 adducts. The DFT study reveals that the latter is more stabilized than the former. The X-ray crystal structure of 1 shows that the packing of the trinuclear unit is controlled by unconventional C-H center dot center dot center dot O H-bonds and Cu(2+)-pi non-covalent interactions. These interactions explain the formation of 1 which is a priori disfavored with respect to 2.

Syntheses, characterization and X-ray crystal structures of a mono- and a penta-nuclear nickel(II) complex with oximato Schiff base ligands

A mononuclear octahedral nickel(II) complex [Ni(HL(1))(2)](SCN)(2) (1) and an unusual penta-nuclear complex [{(NiL(2))(mu-SCN)}(4)Ni(NCS)(2)]center dot 2CH(3)CN (2) where HL(1) = 3-(2-aminoethylimino)butan-2-one oxime and HL(2) = 3-(hydroxyimino)butan-2-ylidene)amino)propylimino)butan-2-one oxime have been prepared and characterized by X-ray crystallography. The mono-condensed ligand, HL(1), was prepared by the 1:1 condensation of the 1,2-diaminoethane with diacetylmonoxime in methanol under high dilution. Complex 1 is found to be a mer isomer and the amine hydrogen atoms are involved in extensive hydrogen bonding with the thiocyanate anions. The dicondensed ligand, HL(2), was prepared by the 1:2 condensation of the 1,3-diaminopropane with diacetylmonoxime in methanol. The central nickel(II) in 2 is coordinated by six nitrogen atoms of six thiocyanate groups, four of which utilize their sulphur atoms to connect four NiL2 moieties to form a penta-nuclear complex and it is unique in the sense that this is the first thiocyanato bridged penta-nuclear nickel(II) compound with Schiff base ligands.

Structural and magnetic studies of Schiff base complexes of nickel(ii) nitrite: change in crystalline state, ligand rearrangement and a very rare μ-nitrito-1κO:2κN:3κO′ bridging mode

Four new nickel(II) complexes, [Ni2L2(NO2)2]·CH2Cl2·C2H5OH, 2H2O (1), [Ni2L2(DMF)2(m-NO2)]ClO4·DMF (2a), [Ni2L2(DMF)2(m-NO2)]ClO4 (2b) and [Ni3L¢2(m3-NO2)2(CH2Cl2)]n·1.5H2O (3) where HL = 2-[(3-amino-propylimino)-methyl]-phenol, H2L¢ = 2-({3-[(2-hydroxy-benzylidene)-amino]-propylimino}-methyl)-phenol and DMF = N,N-dimethylformamide, have been synthesized starting with the precursor complex [NiL2]·2H2O, nickel(II) perchlorate and sodium nitrite and characterized structurally and magnetically. The structural analyses reveal that in all the complexes, NiII ions possess a distorted octahedral geometry. Complex 1 is a dinuclear di-m2-phenoxo bridged species in which nitrite ion acts as chelating co-ligand. Complexes 2a and 2b also consist of dinuclear entities, but in these two compounds a cis-(m-nitrito-1kO:2kN) bridge is present in addition to the di-m2-phenoxo bridge. The molecular structures of 2a and 2b are equivalent; they differ only in that 2a contains an additional solvated DMF molecule. Complex 3 is formed by ligand rearrangement and is a one-dimensional polymer in which double phenoxo as well as m-nitrito-1kO:2kN bridged trinuclear units are linked through a very rare m3-nitrito-1kO:2kN:3kO¢ bridge. Analysis of variable-temperature magnetic susceptibility data indicates that there is a global weak antiferromagnetic interaction between the nickel(II) ions in four complexes, with exchange parameters J of -5.26, -11.45, -10.66 and -5.99 cm-1 for 1, 2a, 2b and 3, respectively

Ternary erbium chromium sulfides : structural relationships and magnetic properties

Single crystals of four erbium-chromium sulfides have been grown by chemical vapor transport using iodine as the transporting agent. Single-crystal X-ray diffraction reveals that in Er(3)CrS(6) octahedral sites are occupied exclusively by Cr(3+) cations, leading to one-dimensional CrS(4)(5-) chains of edge-sharing octahedra, while in Er(2)CrS(4), Er(3+), and Cr(2+) cations occupy the available octahedral sites in an ordered manner. By contrast, in Er(6)Cr(2)S(11) and Er(4)CrS(7), Er(3+) and Cr(2+) ions are disordered over the octahedral sites. In Er(2)CrS(4), Er(6)Cr(2)S(11), and Er(4)CrS(7), the network of octahedra generates an anionic framework constructed from M(2)S(5) slabs of varying thickness, linked by one-dimensional octahedral chains. This suggests that these three phases belong to a series in which the anionic framework may be described by the general formula [M(2n+1)S(4n+3)](x-), with charge balancing provided by Er(3+) cations located in sites of high-coordination number within one-dimensional channels defined by the framework. Er(4)CrS(7), Er(6)Cr(2)S(11), and Er(2)CrS(4) may thus be considered as the n = 1, 2, and infinity members of this series. While Er(4)CrS(7) is paramagnetic, successive magnetic transitions associated with ordering of the chromium and erbium sub-lattices are observed on cooling Er(3)CrS(6) (T(C)(Cr) = 30 K; T(C)(Er) = 11 K) and Er(2)CrS(4) (T(N)(Cr) = 42 K, T(N)(Er) = 10 K) whereas Er(6)Cr(2)S(11) exhibits ordering of the chromium sub-lattice only (T(N) = 11.4 K).

Ozone climatology using interactive chemistry: results from the Canadian Middle Atmosphere Model

The climatology of ozone produced by the Canadian Middle Atmosphere Model (CMAM) is presented. This three-dimensional global model incorporates the radiative feedbacks of ozone and water vapor calculated on-line with a photochemical module. This module includes a comprehensive gas-phase reaction set and a limited set of heterogeneous reactions to account for processes occurring on background sulphate aerosols. While transport is global, photochemistry is solved from about 400 hPa to the top of the model at ∼95 km. This approach provides a complete and comprehensive representation of transport, emission, and photochemistry of various constituents from the surface to the mesopause region. A comparison of model results with observations indicates that the ozone distribution and variability are in agreement with observations throughout most of the model domain. Column ozone annual variation is represented to within 5–10% of the observations except in the Southern Hemisphere for springtime high latitudes. The vertical ozone distribution is generally well represented by the model up to the mesopause region. Nevertheless, in the upper stratosphere, the model generally underestimates the amount of ozone as well as the latitudinal tilting of ozone isopleths at high latitude. Ozone variability is analyzed and compared with measurements. The comparison shows that the phase and amplitude of the seasonal variation as well as shorter timescale variations are well represented by the model at various latitudes and heights. Finally, the impact of incorporating ozone radiative feedback on the model climatology is isolated. It is found that the incorporation of ozone radiative feedback results in a cooling of ∼8 K in the summer stratopause region, which corrects a warm bias that results when climatological ozone is used.

[C7H10N][In3Se5]: a layered selenide with two indium coordination environments

A new layered indium selenide, [C7H10N][In3Se5], was prepared under solvothermal conditions using 3,5-dimethylpyridine as a structure-directing agent. The crystal structure contains anionic layers of stoichiometry [In3Se5]− in which indium atoms with octahedral and tetrahedral coordination coexist. This material represents the first occurrence of octahedrally coordinated indium in a solvothermally-prepared indium selenide.

Long-run restrictions and survey forecasts of output, consumption and investment

We consider the extent to which long-horizon survey forecasts of consumption, investment and output growth are consistent with theory-based steady-state values, and whether imposing these restrictions on long-horizon forecasts will enhance their accuracy. The restrictions we impose are consistent with a two-sector model in which the variables grow at different rates in steady state. The restrictions are imposed by exponential-tilting of simple auxiliary forecast densities. We show that imposing the consumption-output restriction yields modest improvements in the long-horizon output growth forecasts, and larger improvements in the forecasts of the cointegrating combination of consumption and output: the transformation of the data on which accuracy is assessed plays an important role.

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.