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L2
Terms modified by L2 Selected AbstractsInteraction between a dislocation and monovalent anion in various alkali halide crystalsCRYSTAL RESEARCH AND TECHNOLOGY, Issue 10 2010Y. KohzukiArticle first published online: 30 AUG 2010 Abstract It was investigated from (L0/L)2 versus ,0 curve that the Friedel relation between the effective stress and the average length of dislocation segments, L, is appropriate for the interaction between a dislocation and the monovalent anion in various alkali halides single crystals (NaCl: Br - , NaBr: Cl - or I - , KCl: Br - or I - , and RbCl: Br - or I - ). Here, L0 represents the average spacing of monovalent anions on a slip plane and ,0 is the bending angle at which the dislocation breaks away from the anion at the temperature of 0 K. This is because the anions are the weak obstacles such as impede the dislocation at ,0 above about 150 degrees, where the Friedel relation agrees with the Fleischer one (L02 = L2(,,,0)/2). Furthermore, the values of (L /L0) were found to be within 4.05 to 5.87 for the crystals. (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Drosophila NAB (dNAB) is an orphan transcriptional co-repressor required for correct CNS and eye developmentDEVELOPMENTAL DYNAMICS, Issue 1 2003Mark Clements Abstract The mammalian NAB proteins have been identified previously as potent co-repressors of the EGR family of zinc finger transcription factors. Drosophila NAB (dNAB), like its mammalian counterparts, binds EGR1 and represses EGR1-mediated transcriptional activation from a synthetic promoter. In contrast, dNAB does not bind the Drosophila EGR-related protein klumpfuss. dnab RNA is expressed exclusively in a subset of neuroblasts in the embryonic and larval central nervous system (CNS), as well as in several larval imaginal disc tissues. Here, we describe the creation of targeted deletion mutations in the dnab gene and the identification of additional, EMS-induced dnab mutations by genetic complementation analysis. Null alleles in dnab cause larval locomotion defects and early larval lethality (L1,L2). A putative hypomorphic allele in dnab instead causes early adult lethality due to severe locomotion defects. In the dnab -/- CNS, axon outgrowth/guidance and glial development appear normal; however, a subset of eve+ neurons forms in reduced numbers. In addition, mosaic analysis in the eye reveals that dnab -/- clones are either very small or absent. Similarly, dNAB overexpression in the eye causes eyes to be very small with few ommatidia. These dramatic eye-specific phenotypes will prove useful for enhancer/suppressor screens to identify dnab-interacting genes. © 2002 Wiley-Liss, Inc. [source] Effects of locomotor stimulation and protein synthesis inhibition on circadian rhythms in size changes of L1 and L2 interneurons in the fly's visual systemDEVELOPMENTAL NEUROBIOLOGY, Issue 11 2007Elzbieta Kula Abstract Axons of monopolar cell interneurons L1 and L2 in the first optic lobe (lamina) of the fly Musca domestica undergo cyclical changes in diameter. These axons swell during the day and shrink during the night. In addition, the axons' size depends on light conditions since they are largest in continuous light (LL), somewhat smaller under day/night (LD) conditions, and smallest under constant darkness (DD). In this study we found that sizes of both cells can further increase in free flying flies under LD conditions, while the visual stimulation alone does not have significant effect on the cross-sectional area of L1 and L2 axons. The stimulation of free flying had no effect on L1 and L2 sizes if it was performed at the beginning of subjective day in LL or DD. Our results indicate that a maximal increase in size of L1 and L2 is observed when stimulation of free flying is synchronized with a fly' daily peak of activity. We also found that protein synthesis is needed to increase size of monopolar cell axons during the day when they normally swell. © 2007 Wiley Periodicals, Inc. Develop Neurobiol, 2007. [source] Peripheral coding of bitter taste in DrosophilaDEVELOPMENTAL NEUROBIOLOGY, Issue 2 2003Nicolas Meunier Abstract Taste receptors play a crucial role in detecting the presence of bitter compounds such as alkaloids, and help to prevent the ingestion of toxic food. In Drosophila, we show for the first time that several taste sensilla on the prothoracic legs detect bitter compounds both through the activation of specific taste neurons but also through inhibition of taste neurons activated by sugars and water. Each sensillum usually houses a cluster of four taste neurons classified according to their best stimulus (S for sugar, W for Water, L1 and L2 for salts). Using a new statistical approach based on the analysis of interspike intervals, we show that bitter compounds activate the L2 cell. Bitter-activated L2 cells were excited with a latency of at least 50 ms. Their sensitivity to bitter compounds was different between sensilla, suggesting that specific receptors to bitter compounds are differentially expressed among L2 cells. When presented in mixtures, bitter compounds inhibited the responses of S and W, but not the L1 cell. The inhibition was effective even in sensilla where bitter compounds did not activate the L2 cell, indicating that bitter compounds directly interact with the S and W cells. Interestingly, this inhibition occurred with latencies similar to the excitation of bitter-activated L2 cells. It suggests that the inhibition in the W and S cells shares similar transduction pathways with the excitation in the L2 cells. Combined with molecular approaches, the results presented here should provide a physiological basis to understand how bitter compounds are detected and discriminated. © 2003 Wiley Periodicals, Inc. J Neurobiol 56: 139,152, 2003 [source] Dyslexia in English as a second languageDYSLEXIA, Issue 1 2005Turid Helland Abstract This study focused on English as L2 in a group of Norwegian dyslexic 12 year olds, compared to an age and gender matched control group. Norwegian school children learn English from the first grades on. The subjects were assessed with a test battery of verbal and written tasks. First, they were given a comprehension task; second, a model sentence task; third, two pragmatic tasks, and fourth, three tasks of literacy. The verbal tasks were scored according to comprehension, morphology, syntax and semantics, while the literacy tasks were scored by spelling, translation and reading skills. It was hypothesized that the results of the control group and the dyslexia group would differ on all tasks, but that subgrouping the dyslexia group by comprehension skills would show heterogeneity within the dyslexia group. The data analyses confirmed these hypotheses. Significant differences were seen between the dyslexia group and the control group. However, the subgrouping revealed minor differences between the control group and the subgroup with good comprehension skills, and major differences between the control group and the subgroup with poor comprehension skills. Especially morphology and spelling were difficult for the dyslexia group. The results were tentatively discussed within the framework of biological and cognitive models of how to interpret L2 performance in dyslexia, underlining the importance of further research in L2 acquisition in dyslexia. Copyright © 2004 John Wiley & Sons, Ltd. [source] OUTSOURCING AND UNIONIZATION: A TALE OF MISALLOCATED (RESISTANCE) RESOURCESECONOMIC INQUIRY, Issue 2 2010ELISABETTA MAGNANI While many believe the growth in outsourcing contributed to the decline in U.S. unionization up to the 1990s, this argument has never been investigated systematically. In this article, we analyze the effect of outsourcing on unionization between 1973 and 1993. Instrumental variables estimation shows outsourcing contributes to higher quasirents and industry productivity. We find the union wage premium increases with the extent of outsourcing,both for workers that are substitutable by outsourcing services and workers in jobs that are not substitutes of the tasks being outsourced. Finally, we find no support for the claim that outsourcing reduces unionization. (JEL J5, L2, L6) [source] FIXED REVENUE AUCTIONS: THEORY AND BEHAVIORECONOMIC INQUIRY, Issue 3 2008CARY A. DECK In this paper, we study auctions in which the revenue is fixed but the quantity is determined by the auction mechanism. Specifically, we investigate the theory and behavior of English quantity clock, Dutch quantity clock, last-quantity sealed bid, and penultimate-quantity sealed bid auctions. For theoretically equivalent fixed quantity and fixed revenue auctions, we find that fixed revenue auctions are robust to all the previously observed empirical regularities in fixed quantity auctions. (JEL C9, D4, L2) [source] Intralesional bovine papillomavirus DNA loads reflect severity of equine sarcoid diseaseEQUINE VETERINARY JOURNAL, Issue 4 2010R. HARALAMBUS Summary Reasons for performing study: Sarcoids are nonmetastasising, yet locally aggressive skin tumours that constitute the most frequent neoplasm in equids. Infection by bovine papillomaviruses types 1 and 2 (BPV-1, BPV-2) has been recognised as major causative factor in sarcoid pathogenesis, but a possible correlation of intralesional virus load with disease severity has not been established thus far. Hypothesis: Given the pathogenic role of BPV-1 and BPV-2 in sarcoid disease, we suggest that intralesional viral DNA concentration may reflect the degree of affection. Methods: Severity of disease was addressed by recording the tumour growth kinetics, lesion number and tumour type for 37 sarcoid-bearing horses and one donkey. Viral load was estimated via quantitative real-time PCR (qPCR) of the E2, E5, L1 and L2 genes from the BPV-1/-2 genome for one randomly selected lesion per horse and correlated with disease severity. Results: Quantitative PCR against E2 identified viral DNA concentrations ranging from 0,556 copies/tumour cell. Of 16 horses affected by quiescent, slowly growing single tumours or multiple mild-type lesions, 15 showed a viral load up to 1.4 copies per cell. In stark contrast, all equids (22/22) bearing rapidly growing and/or multiple aggressive sarcoids had a viral load between 3 and 569 copies per cell. Consistent results were obtained with qPCR against E5, L1 and L2. Conclusions: While tumours of the same clinical type carried variable virus load, confirming that viral titre does not determine clinical appearance, we identified a highly significant correlation between intralesional viral load and disease severity. Potential relevance: The rapid determination of BPV viral load will give a reliable marker for disease severity and may also be considered when establishing a therapeutic strategy. [source] Effect of local analgesia on movement of the equine backEQUINE VETERINARY JOURNAL, Issue 1 2006K. ROETHLISBERGER HOLM Summary Reasons for performing study: Diagnostic infiltration of local anaesthetic solution is commonly used in cases of equine back pain. Evaluation is subjective and it is not known how local analgesia of the back affects horses without clinical signs of back pain. Objectives: To evaluate the effect of infiltration of local anaesthetics on the movement of the back in horses without clinical signs of back pain, and to evaluate the usefulness of kinematic studies as an objective and quantitative tool in evaluating local analgesia in clinical practice. Methods: The kinematics of the back in 10 clinically sound horses were measured on 2 occasions at walk and trot before and after injections with mepivacaine and sodium chloride around the interspinous spaces between T16 and L2. The kinematics were compared between the 2 occasions before injections and before and after each injection. Results: The range of motion (ROM) for dorsoventral flexion-extension (FE) of the back was increased significantly in all measured segments other than T10 at walk, as was lateral bending (LB) at T10, L3 and L5 after injection of mepivacaine. For lateral excursion (LE), total movement increased at all measured segments. At trot the only affected segment was L3, where the injection with mepivacaine decreased the ROM for FE. After injection of sodium chloride the ROM for FE increased at T13 and T17 at walk. Lateral bending and LE were not affected at walk. At trot, LB increased at L3 and L5. Conclusions and potential relevance: Diagnostic infiltration of local anaesthetic solution affects the function of the back in clinically sound horses, which must be considered when interpreting the use of this clinical aid in assessing clinical cases of back dysfunction. Kinematics can qualitatively and quantitatively evaluate the effect of local analgesia of the back. [source] Bis(terdentate) Pyrazole/Pyridine Ligands: Synthesis, Crystal Structures and Magnetic Properties of Bridged Binuclear and Tetranuclear Copper(II) ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2009Akhilesh Kumar Singh Abstract A new binucleating bis(terdentate) ligand, 3,5-[3-bis(2-pyridyl)pyrazole-1-ylmethyl]pyrazole (HL2), was synthesized. Reaction of the deprotonated ligand L2 with hydrated CuII salts gives (,-pyrazolato)(,-hydroxido)-bridged binuclear and tetranuclear complexes [L2Cu2(,-OH)(ClO4)(MeCN)](ClO4) (2), [L2Cu2(dmf)2(,3 -OH)]2(ClO4)4·4dmf (3·4dmf) and [L2L,Cu2](ClO4)2 [4; HL, = 3-(2-pyridyl)pyrazole]. In these complexes, both ,-OH and ,3 -OH bridges were observed. This contrasts the situation for a dicopper(II) complex of the related bis(terdentate) ligand 3,5-bis[6(2,2,-dipyridyl)]pyrazole (HL1), {L1Cu2(OMe)(MeOH)[,1 - O -(NO3)]}{[Cu2(NO3)2(,-OMe)2]}0.5·MeOH (1·MeOH), where the shorter and more rigid ligand side arms enforce a larger Cu···Cu separation and the formation of a MeO,HOMe moiety within the bimetallic pocket. Molecular structures of all complexes were elucidated by X-ray crystallography. Variable-temperature magnetic susceptibility measurements (295,2 K) for powdered samples of complexes 2,4 reveal strong antiferromagnetic coupling between two copper centres. The magnitude of the coupling is discussed in view of the structural features. During the preparation of complex 4, partial ligand hydrolysis was also observed, but this strongly depends on the reaction conditions.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] A Chiral Metal,Organic Framework Based on Heptanuclear Zinc CoresEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2009Hai-Yang Liu Abstract Two zinc(II) complexes, [Zn9(L1)6(H2O)2]·13.5H2O (1) and [Zn9(L2)6(H2O)3]·C2H5OH·8.5H2O (2), were synthesized. Both 1 and 2 are constructed from molecular building units (MBUs) that contain heptanuclear zinc clusters as cores. By introducing an additional chiral site into the original ligand, we achieved the transformation of the MOF from a nonchiral to a chiral structure, which provides a new strategy for designing chiral compounds. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Self-Assembly from Discrete Clusters to 2D Network Based on [Fe(phen)(CN)4], and [Fe(bipy)(CN)4],: Synthesis, Structures and Magnetic PropertiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2009Hua Xiang Abstract A series of cyanido-bridged complexes {[FeIII(phen) (CN)4]2[NiL1]}·4H2O (1), {[FeIII(bipy)(CN)4]2[NiL1]}·4H2O (2), [FeIII(bipy)(CN)4]2[NiL2] (3), {[FeIII(phen)(CN)4]2[CuL3]}·5H2O (4), {[FeII(phen)(CN)4][Ni(ea)2]}2·2H2O (5), {[FeII(phen)(CN)4] [NiL2]·2H2O}n (6), {[FeIII(bipy)(CN)4]2[Ni(H2O)2]}·6.5H2O}n (7) and {[FeII(bipy)(CN)4][Ni(ea)2]·H2O}n (8) were synthesized using H[Fe(phen)(CN)4]·2H2O and H[Fe(bipy)(CN)4]·2H2O as precursors [L1 = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, L2 = 3,10-bis(2-phenylethyl)-1,3,5,8, 10,12-hexaazacyclotetradecane, L3 = 3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane, phen = 1,10-phenanthroline, bipy = 2,2,-bipyridine, ea = ethanolamine). Complexes 1,4 are trinuclear clusters, and 5 is a tetranuclear square. In 6, the [FeII(phen)(CN)4]2, anions alternately bridge the [NiL2]2+ cations to generate a 1D wavy chain. The structure of 7 possesses a 4,2-ribbonlike chain, which contains a NiII2(CN)4FeIII2 square with each NiII atom shared by two adjacent squares. Each FeII and NiII atom in 8 acts as a three-connected node through the cyanido-bridges to generate a 2D network with a 4,82 topological net. Ferromagnetic couplings are found between the low-spin FeIII ions and the NiII ions through the cyanido groups in 1,3 and 7, and a metamagnetic behavior and a frequency dependence of the out-of-phase ac susceptibility are observed in 7. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Toward an Allosteric Metallated ContainerEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2009Helga Szelke Abstract Polytopic ligands L1 and L2 in which three 2,2,-bipyridine units are linked to a central tris(pyrid-2-yl)amine (L1) or tris(pyrid-2-yl)methanol (L2) moiety by alkyl spacers were prepared by multistep organic syntheses. The parent tris(pyrid-2-yl)-type ligands were shown to be modest-to-good chelators for Zn2+ and Cu2+ ions in solution, and bi- and tridentate N-coordination was confirmed by crystal structures of CuII and RuII complexes, respectively. FeII and RuII smoothly form stable, cage-like 1:1 complexes with L1 and L2, in which the metal ion is coordinated to the tris(bpy) site of the ligands. The vacant tris(pyrid-2-yl) site of these complexes is, however, a poor donor site for Zn2+ and Cu2+ ions. In addition, FeII modulates the coordination behaviour of the tris(pyrid-2-yl) site toward Zn2+: Whereas tris(5-methylpyrid-2-yl)amine forms a 2:1 complex with Zn2+ in CH2Cl2, [Fe(L1)]2+ forms a 1:1 Zn complex. Spectrophotometric titrations suggest that [Fe(L2)]2+ forms a polynuclear Zn2+ complex in CH2Cl2, possibly involving bridging coordination of the alcohol OH group, which contrasts the smooth formation of a 2:1 complex of the parent tris(pyrid-2-yl)-type ligand with Zn. FeII might therefore be considered as an allosteric effector, which modulates the metal binding properties of the second tris(pyrid-2-yl) site of L1 and L2. Contrary to expectation, Zn2+ and Cu2+ appear to associate weakly with donor atoms directed toward the exterior of the cage-like complexes [Fe(Ln)]2+ and [Ru(L1)]2+, rather than locating in the interior of the container by tripodal coordination to the tris(pyrid-2-yl) site.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Synthesis, Protonation and CuII Complexes of Two Novel Isomeric Pentaazacyclophane Ligands: Potentiometric, DFT, Kinetic and AMP Recognition StudiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2009Andrés G. Algarra Abstract The synthesis and coordination chemistry of two novel ligands, 2,6,9,12,16-pentaaza[17]metacyclophane (L1) and 2,6,9,12,16-pentaaza[17]paracyclophane (L2), is described. Potentiometric studies indicate that L1 and L2 form a variety of mononuclear complexes the stability constants of which reveal a change in the denticity of the ligand when moving from L1 to L2, a behaviour that can be qualitatively explained by the inability of the paracyclophanes to simultaneously use both benzylic nitrogen atoms for coordination to a single metal centre. In contrast, the formation of dinuclear hydroxylated complexes is more favoured for the paraL2 ligand. DFT calculations have been carried out to compare the geometries and relative energies of isomeric forms of the [CuL]2+ complexes of L1 and L2 in which the cyclophane acts either as tri- or tetradentate. The results indicate that the energy cost associated with a change in the coordination mode of the cyclophane from tri- to tetradentate is moderate for both ligands so that the actual coordination mode can be determined not only by the characteristics of the first coordination sphere but also by the specific interactions with additional nearby water molecules. The kinetics of the acid promoted decomposition of the mono- and dinuclear CuII complexes of both cyclophanes have also been studied. For both ligands, dinuclear complexes convert rapidly to mononuclear species upon addition of excess acid, the release of the first metal ion occurring within the mixing time of the stopped-flow instrument. Decomposition of the mononuclear [CuL2]2+ and [CuHL2]3+ species occurs with the same kinetics, thus showing that protonation of [CuL2]2+ occurs at an uncoordinated amine group. In contrast, the [CuL1]2+ and [CuHL1]3+ species show different decomposition kinetics indicating the existence of significant structural reorganisation upon protonation of the [CuL1]2+ species. The interaction of AMP with the protonated forms of the cyclophanes and the formation of mixed complexes in the systems Cu,L1 -AMP, Cu,L2 -AMP, and Cu,L3 -AMP, where L3 is the related pyridinophane containing the same polyamine chain and 2,6-dimethylpyridine as a spacer, is also reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Pseudo-Octahedral Schiff Base Nickel(II) Complexes: Does Single Oxidation Always Lead to the Nickel(III) Valence Tautomer?EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 27 2008Olaf Rotthaus Abstract With the aim of establishing correlations between the ligand structure and the oxidation site in nickel complexes from Schiff base ligands, five ligands and their nickel complexes have been synthesized. The prototypical asymmetric Schiff base ligand HL1 contains both phenol and pyridine pendant arms with a pivotal imine nitrogen atom. Ligands HL2,5 differ from HL1 by either their phenolate para substituent, the hybridization of the pivotal nitrogen atom, and/or the N-donor properties of the pyridine moiety. The five complexes [Ni(L1,5)2] are obtained by treating the corresponding ligands with 0.5 equiv. of Ni(OAc)2·4H2O in the presence of NEt3. X-ray crystal-structure diffraction studies as well as DFT calculations reveal that [Ni(L1,5)2] involves a high-spin nickel(II) ion within a pseudo-octahedral geometry. The two ligands are arranged in a meridional fashion when the pivotal nitrogen atom is an imine {as in [Ni(L1,2)2] and [Ni(L4,5)2]}, while the fac isomer is preferred in [Ni(L3)2] (amino pivotal nitrogen atom). [Ni(L1)2] is characterized by an oxidation potential at ,0.17 V vs. Fc+/Fc. The one-electron-oxidized species [Ni(L1)2]+ exhibits an EPR signal at g = 2.21 attributed to a phenoxyl radical that is antiferromagnetically coupled to a high-spin NiII ion. [Ni(L2)2] differs from [Ni(L1)2] by the phenolate para substituent (a tert -butyl instead of the methoxyl group) and exhibits an oxidation potential that is ca. 0.16 V higher. Compared to [Ni(L1)2]+ the cation [Ni(L2)2]+ exhibits a SOMO that is more localized on the metal atom. The EPR and electrochemical signatures of [Ni(L3)2]+ are similar to those of [Ni(L1)2]+, thus showing that an imino to amino substitution compensates for a methoxy to tert -butyl one. Replacement of the pyridine by a quinoline group in [Ni(L4,5)2] makes the complexes slightly harder to oxidize. The EPR signatures of the cations [Ni(L4,5)2]+ are roughly similar to those of the pyridine analogs [Ni(L1,2)2]+. The oxidation site is thus not significantly affected by changes in the N-donor properties of the terminal imino nitrogen atom.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Spectroscopic and Computational Study on New Blue Emitting ReL(CO)3Cl Complexes Containing Pyridylimidazo[1,5- a]pyridine LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2008Claudio Garino Abstract The structural and photophysical properties of three new ReL(CO)3Cl complexes (ReL1,ReL3) and their 1-(2-pyridyl)imidazo[1,5- a]pyridine ligands, namely 3-methyl-1-(2-pyridyl)imidazo[1,5- a]pyridine (L1), 1-(2-pyridyl)-3-[4-(trifluoromethyl)phenyl]imidazo[1,5- a]pyridine (L2), and 3-(4-nitrophenyl)-1-(2-pyridyl)imidazo[1,5- a]pyridine (L3), were studied by spectroscopy, X-ray diffraction, and computational methods. ReL1,ReL3 have high-energy singlet emissions arising from a , , ,* ligand-centered state. In oxygen-free acetonitrile solutions, the complexes display dual fluorescence due to intense ligand-centered triplet emission.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Using Chiral Ligand Substituents To Promote the Formation of Dinuclear, Double-Stranded Iron, Manganese, and Zinc MesocatesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 33 2007Stuart D. Reid Abstract The synthesis and structures of dinuclear manganese, iron, and zinc complexes of chiral di-iminodipyrromethane ligands (L) are reported. Schiff base condensation reactions between 5,5,-diformyl-2,2,-dipyrromethane and the chiral amines (,)-(R)-CH(Me)tBu and (+)-(R)-CH(Me)Ph result in the straightforward synthesis of the new, chiral ligands H2L2 and H2L3, respectively. Salt elimination reactions between K2L and divalent Mn and Fe halides, and protonolysis reactions between ZnMe2 and H2L result in the formation of the new dinuclear complexes [M2(L)2]. Investigation of the structures of these compounds in solution and in the solid state reveal that chiral mesocates are formed for L = L2, whereas for L = L3, a racemic mixture of helicates is present.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Nickel Complexes with N2O Donor Ligands: Syntheses, Structures, Catalysis and Magnetic StudiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 32 2007Jishnunil Chakraborty Abstract Two new terephthalato-bridged tetranuclear polymeric NiII complexes, namely [Ni4L41(,-tp-,4 -O)(H2O)2(,-tp-,2 -O)]·2C2H5OH·CH3OH·3H2O (1) and [Ni4L42(,-tp-,4 -O)(H2O)2(,-tp-,2 -O)]·3H2O (2) [L1 = N -(3-aminopropyl)-5-bromosalicylaldimine and L2 = N -(3-aminopropyl)salicylaldimine], are reported along with the syntheses and structures of the dicyanoargentate-bridged polymeric complexes [Ni(L1)(H2O){Ag(CN)2}], (3) and [Ni(L3)(MeOH){Ag(CN)2}], (4) [L3 = N -(3-amino-2,2-dimethylpropyl)-5-bromosalicylaldimine]. All four complexes are found to be effective heterogeneous catalysts for the epoxidation of alkenes such as styrene, ,-methylstyrene and cyclohexene in the presence of tert -butyl hydroperoxide. The variable-temperature magnetic susceptibility measurements (300,2 K) of complex 1 show a fair degree of antiferromagnetic coupling between the NiII centers.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Tetranuclear Nickel Complexes Composed of Pairs of Dinuclear LNi2 Fragments Linked by 4,4,-Bipyrazolyl, 1,4-Bis(4,-pyrazolyl)benzene, and 4,4,-Bipyridazine: Synthesis, Structures, and Magnetic PropertiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2007Vasile Lozan Abstract The ability of the ligands 4,4,-bipyrazolyl (H2bpz), 1,4-bis(4,-pyrazolyl)benzene (H2bpzb), and 4,4,-bipyridazine (bpdz) to link two dioctahedral LNi2 units has been examined. Thefollowing complexes were prepared: [L1NiII2(Hbpz)][BPh4] (6[BPh4]), [L1NiII2(bpdz)][ClO4]2 (7[ClO4]2), [(L1NiII2)2(bpzb)][BPh4]2 (8[BPh4]2), and [(L2NiII2)2(bpz)][BPh4]2 (9[BPh4]2), where (L1)2, and (L2)2, represent macrocyclic hexaaza-dithiophenolate ligands. All complexes have been characterised by UV/Vis spectroscopy, IR spectroscopy, and X-ray crystallography. Whereas (Hbpz), and bpdz in 6[BPh4]2 and 7[ClO4]2 act as bidentate ligands coordinating to only one [LNi2]2+ unit, in 8[BPh4]2 and 9[BPh4]2 the (bpzb)2, and(bpz)2, units are tetradentate linkers. This is qualitatively explained in terms of the absence or presence of steric repulsions between the tBu groups of the supporting ligands and the length of the coligands. The structures of the tetranuclear complexes differ mainly in the distance between the center of the Ni···Ni axes of the isostructural [LNi2] units {14.040(1) Å in 8[BPh4]2, 9.184(1) Å in 9[BPh4]2}. The two Ni2pyrazolato planes in 9[BPh4]2 are coplanar. An analysis of the temperature-dependent magnetic susceptibility data for 9[BPh4]2 reveals the presence of weak ferromagnetic exchange interactions between the NiII ions in the binuclear [L2Ni2] subunits with values for the magnetic exchange constant J1 of 23.97 cm,1 (H = ,2JS1S2). The exchange coupling across the dipyrazolato bridge is less than 0.1 cm,1, suggesting that no significant interdimer exchange coupling occurs in 9[BPh4]2. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Metal Ion Complementarity: Effect of Ring-Size Variation on the Conformation and Stability of Lead(II) and Cadmium(II) Complexes with Pendant-Armed CrownsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2007Martín Regueiro-Figueroa Abstract The binding tendencies of the pendant-armed crown ethers L1,L3 [L1 = N,N, -bis(benzimidazol-2-ylmethyl)-1,7-diaza-12-crown-4, L2 = N,N, -bis(benzimidazol-2-ylmethyl)-1,10-diaza-15-crown-5) and L3 = N,N, -bis(benzimidazol-2-ylmethyl)-4,13-diaza-18-crown-6] towards PbII and CdII have been investigated. The X-ray crystal structure of [Cd(L3)](ClO4)2·EtOH shows that, in the solid state, the CdII ion is eight-coordinate and fits quite well into the crown hole, favouring an anti arrangement of the organic receptor. NMR measurements recorded in acetonitrile solution indicate that increasing the crown size induces a conformational change in the series of CdII complexes. The conformation goes from a syn arrangement for L1 to an anti arrangement for L3, passing through a syn [lrarr2] anti equilibrium in the complex derived from L2. On the contrary, no conformational change was observed for the corresponding PbII complexes, which have a syn conformation in all cases. These results have been confirmed by means of density functional theory (DFT) calculations performed by using the B3LYP model. The binding constants obtained from UV/Vis titration experiments in DMSO solution demonstrate that a decrease in the crown size provokes a 102 -fold enhancement of the stability for this series of CdII complexes, whereas for PbII a gradual decrease of the binding constants is observed. Receptor L1 shows a certain degree of selectivity for CdII over PbII, with a selectivity factor > 102. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Receptor versus Counterion: Capability of N,N, -Bis(2-aminobenzyl)-diazacrowns for Giving Endo- and/or Exocyclic Coordination of ZnIIEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2007Lea Vaiana Abstract The structure of ZnII complexes with receptors L1 and L2[L1 = N,N, -bis(2-aminobenzyl)-1,10-diaza-15-crown-5 and L2 = N,N, -bis(2-aminobenzyl)-4,13-diaza-18-crown-6] was studied both in the solid state and in acetonitrile solution. Both receptors form mononuclear ZnII complexes in this solvent, while no evidence for the formation of dinuclear complexes was obtained. This is in contrast with previous investigations that demonstrated the formation of dinuclear complexes of L2 with first-row transition metals such as NiII, CoII and CuII. Compounds of formula [Zn(L1)](ClO4)2 (1), [Zn(L1)](NO3)2·2CH3CN (2), [Zn(L2)](ClO4)2 (3) and [Zn(L2)(NO3)2] (4) were isolated and structurally characterised by X-ray diffraction analyses. L1 forms seven-coordinate ZnII complexes in the presence of both nitrate and perchlorate anions, as a consequence of the good fit between the macrocyclic cavity and the ionic radius of the metal ion. The ZnII ion is deeply buried into the receptor cavity and the anions are forced to remain out of the metal coordination sphere. The cation [Zn(L1)]2+ present in 1 and 2 is one of the very few examples of seven-coordinate Zn complexes. Receptor L2 provides a very rare example of a macrocyclic receptor allowing endocyclic and exocyclic coordination on the same guest cation, depending on the nature of the anion present. Thus, in 3 the ZnII ion is endocyclically coordinated, placed inside the crown hole coordinated to four donor atoms of the ligand in a distorted tetrahedral environment, whereas in 4, the presence of a strongly coordinating anion such as nitrate results in an exocyclic coordination of ZnII, which is directly bound only to the two primarily amine groups of L2 and two nitrate ligands. Spectrophotometric titrations of [Zn(L2)]2+ with tetrabutylammonium nitrate in acetonitrile solution demonstrate the stepwise formation of 1:1 and 1:2 adducts with this anion in acetonitrile solution. The [Zn(L1)]2+, [Zn(L2)]2+ and [Zn(L2)(NO3)2] systems were characterised by means of DFT calculations (B3LYP model). The calculated geometries show an excellent agreement with the experimental structures obtained from X-ray diffraction analyses. Calculated binding energies of the macrocyclic ligands to ZnII are also consistent with the experimental data.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] [CuII4] Clusters From the Self-Assembly of Two Imidazolidinyl 2-Phenolate-Bridged [CuII2] Units: The Role of the Chloride BridgeEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2007Alok Ranjan Paital Abstract A new family of tetracopper clusters [Cu4(,4 -X)L2]ClO4·nH2O (1a,c) [X = Cl, Br, I; n = 12, 2, 2; H3L = 2-(2,-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine] have been synthesised and characterised. The X-ray crystal structure of 1a reveals that the template action of the spherical Cl, anion (,4 -Cl,), which features a unique rectangular planar bridging mode, is responsible for the self-assembly of two [Cu2L]+ units in complex 1a. In this family of complexes the spherical halides serve as templates to assemble the dimeric unit into tetrameric complexes, which gives an insight into the role of the halide bridge in tetranuclear complex formation. The capacity of this bridge to mediate magnetic coupling has been examined by bulk magnetic measurements for complex 1a. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Control of Intramolecular Ether-Oxygen Coordination in the Crystal Structure of Copper(II) Complexes With Dipicolylamine-Based LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2007Yuji Mikata Abstract Thirteen crystal structures of copper(II) complexes with a series of dipicolylamine (DPA)-derived ligands, N -(2-methoxyethyl)- N,N -bis(2-pyridylmethyl)amine (L1), N -[2-(2-hydroxyethyloxy)ethyl]- N,N -bis(2-pyridylmethyl)amine (L2) and N -(3-methoxypropyl)- N,N -bis(2-pyridylmethyl)amine (L3), have been determined and the factors that control the coordination of the ether-oxygen atom of these ligands to the copper centre are discussed. Complexes that have +1 or +2 charges exhibit coordination of the ether-oxygen atom, whereas neutral complexes in which two anions are bound to the copper(II) centre tend to lose the oxygen coordination. Upon chelation of the oxygen atom, L3 forms a six-membered chelate ring with respect to the 3-aminopropyl ether moiety whereas L1 and L2 form a five-membered chelate. This difference, especially in the nitrate and bromide complexes, determines whether the ether-oxygen atom chelates to the metal centre to give a monocationic complex, or the second anion coordinates to the metal centre to form the ether-free, neutral complex. The terminal anchor hydroxy group of L2 facilitates the ether-oxygen coordination via a hydrogen bond interaction to the donor atom located trans to the aliphatic nitrogen atom in the basal plane. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Bulky-Hindrance-Controlled Ligand Transformation from Linked Bis(amidinate) to Linked Imido-Amidinate Promoted by a Mono(cyclopentadienyl)titanium GroupEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2006Sheng-Di Bai Abstract A novel class of silyl-linked bis(amidinate) ligands [SiMe2{NC(Ph)N(2,6-R2Ph)Li}2] [L1 (R = H), L2 (R = Me), and L3 (R = iPr)] reacted with TiCl3(C5H5) to produce the half-sandwich titanium complexes 1, 2, and 3. The molecular structures of 1,3 were confirmed successfully by X-ray crystallography. An unprecedented intramolecular ligand transformation from the linked bis(amidinate) configuration to the linked imido-amidinate configuration took place in the cases of L1 and L2. It was found that the rearrangement process was related to the steric hindrance of the terminal substituents. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Synthesis, Crystal Structure, and Second-Order Nonlinear Optical Properties of Ruthenium(II) Complexes with Substituted Bipyridine and Phenylpyridine LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2006Laurence Labat Abstract Two new ruthenium(II) complexes of formula [Ru(bpy)2(L1)][PF6] and [Ru(bpy)2(L2)][PF6]2 are reported. HL1 is a (nitrophenyl)ethenyl-substituted phenylpyridine ligand, and L2 is the bipyridine analogue of HL1. The X-ray crystal structure of [Ru(bpy)2(L1)][PF6] has been solved, and the compound is found to crystallize in the monoclinic C2/c space group. The electronic spectrum of the cyclometalated derivative [Ru(bpy)2(L1)][PF6] exhibits a low-lying transition that is red-shifted from 454 to 546 nm relative to that of the parent bipyridine-based complex, which reveals an important charge-transfer character. To support this assumption, the nonlinear optical properties were investigated by the hyper-Rayleigh scattering technique and indicate a molecular static hyperpolarizability (,0) equal to 230,×,10,30 cm5,esu,1. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Copper Complexes with (2,7-Di- tert -butylfluoren-9-ylidene)methanedithiolate: Oxidatively Promoted Dithioate Condensation,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2006José Vicente Abstract The reaction of [Cu(NCMe)4]PF6 with piperidinium 2,7-di- tert -butyl-9H -fluorene-9-carbodithioate (pipH)[S2C(tBu-Hfy)] (1; tBu-Hfy = 2,7-di- tert -butylfluoren-9-yl), affords [Cun{S2C(tBu-Hfy)}n] (2), which reacts with various P ligands to give [Cu{S2C(tBu-Hfy)}L2] [L = PPh3 (3a), PCy3 (3b), PiPr3 (3d); L2 = 1,1,-bis(diphenylphosphanyl)ferrocene (dppf, 3c), bis(diphenylphosphanyl)methane (dppm, 3e)]. Compounds 3a,c react with atmospheric oxygen and moisture in the presence of NEt3 to give the dinuclear complexes [Cu2{[SC=(tBu-fy)]2S}L2] [tBu-fy = 2,7-di- tert -butylfluoren-9-ylidene; L = PPh3 (4a), PCy3 (4b); L2 = dppf (4c)], which contain a new dithiolato ligand formally resulting from the condensation of two dithioato ligands with loss of a sulfide ion and two protons. Neutral CuI dithiolate complexes of the type [Cu4{S2C=(tBu-fy)}2L4] [S2C=(tBu-fy) = [2,7-di- tert -butylfluoren-9-ylidene)methanedithiolate; L = PPh3 (5a), P(C6H4OMe- p)3 (5b), PiPr3 (5d) or L2 = dppf (5c)] were obtained by treating 1 with [Cu(NCMe)4]PF6, the corresponding phosphane, and piperidine in a 1:2:2:1 molar ratio. The reaction of 1 with Cu(ClO4)2·6H2O and (Pr4N)OH in a 2:1:2 molar ratio gives the CuII complex (Pr4N)2[Cu{S2C=(tBu-fy)}2] [(Pr4N)26], which readily oxidizes to the CuIII complex Pr4N[Cu{S2C=(tBu-fy)}2] (Pr4N7) in the presence of atmospheric oxygen and moisture. The salt PPN7 [PPN+ =(Ph3P)2N+] was obtained from 1, CuCl2·2H2O, PPNCl, and piperidine in a 2:1:1:2 molar ratio under aerobic conditions. The crystal structures of 3a, 3c·CH2Cl2, 4a·4Me2CO, and 4c·CH2Cl2 have been determined by X-ray diffraction studies. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Mono- and Dinuclear CuII and ZnII Complexes of Cyclen-Based Bis(macrocycles) Containing Two Aminoalkyl Pendant Arms of Different LengthsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2005Carmen Anda Abstract The basicity and coordination properties towards CuII and ZnII of the bis(macrocycles) L1, L2 and L3 have been investigated by means of potentiometric, 1H NMR and UV/Vis spectroscopic titrations in aqueous solutions. The synthesis of L1 and L3 is also described. The three ligands are composed of two [12]aneN4 units separated by a p- phenylene spacer and differ in the length of the aminoalkyl pendant arms linked to each macrocyclic unit. L1,L3 form mono- and dinuclear complexes in aqueous solutions; in the dinuclear species each metal ion is coordinated by one of the two identical [12]aneN4 ligand moieties, as shown by the crystal structures of the complexes [Cu2L1]Cl4·8H2O, [Zn2L2](ClO4)4 and [Zn2L3](ClO4)4·H2O. In all structures the metal ion is pentacoordinate, and is bound to the four nitrogen donors of the cyclic unit and to the amine group of the side arm. The stability of both the [ML]2+ and [M2L]4+ complexes in aqueous solution decreases in the order L1 > L2 > L3. At the same time, both the [Cu2L]4+ and [Zn2L]4+ complexes show a different ability in proton binding among the three ligands, with the [M2L1]4+ complexes displaying the highest basicity. These results are explained in terms of the decreasing number of nitrogen donors involved in CuII or ZnII binding on passing from L1 to L3; in other words, while in the L1 dinuclear complexes each metal ion is coordinated to the four amine groups of a [12]aneN4 moiety and to the amine group of the side arm, in the L3 ones the metal cations are bound only to the four donor atoms of a cyclic moiety, the aminobutyl group not being coordinated. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Syntheses and Properties of Metal-Centered Mixed-Valent [NEt4]{MnII,[MnII3MnIII3Cl6(L)6]} Manganese WheelsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 6 2005Rolf W. Saalfrank Abstract Upon reaction of N -substituted diethanolamines H2L2,4 (4, 6, 7) with cesium carbonate and bis(tetraethylammonium) tetrachloromanganate(II) in acetonitrile in the presence of air, the metal-centered mixed-valent manganese wheels [NEt4]{MnII,[MnII3MnIII3Cl6(L2,4)6]} (8,10) were generated. X-ray crystallographic structure analyses revealed, that 8,10 are principally isostructural and consist of an alternating ring of three MnII and three MnIII ions, centered by an additional MnII ion. The cyclic voltammograms of 8 and 10 displayed three quasi-reversible oxidation processes, which are attributed to the subsequent one electron-oxidations of the three peripheral MnII ions to MnIII. Oxidation of the central MnII ion is not observed within the applied potential. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Tellurated Schiff Bases Formed from {2-[(4-Methoxyphenyl)telluro]ethyl}amine and Bis(2-aminoethyl) Telluride with o -Hydroxyacetophenone: Synthesis and Complexation Reactions with HgII, PdII and RuII , Crystal Structures of the Ligands, [Ru(p -cymene)Cl{H2NCH2CH2TeC6H4 -4-OCH3}]Cl·H2O and [RuCl{4-MeOC6H4TeCH2CH2NHCH(CH3)C6H4 -2-O,}]EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2004Raghavendra Kumar P. Abstract {2-[(4-Methoxyphenyl)telluro]ethyl}amine and bis(2-aminoethyl) telluride on treatment with o -hydroxyacetophenone gave the Schiff bases 4-MeOC6H4TeCH2CH2N=C(CH3)C6H4 -2-OH (L1) and 2-HOC6H4(CH3)C=NCH2CH2TeCH2CH2N=C(CH3)C6H4 -2-OH (L3), respectively. The reduction of L1 and L3 with NaBH4 resulted in 4-MeOC6H4TeCH2CH2NHCH(CH3)C6H4 -2-OH (L2) and 2-HOC6H4(CH3)CHNHCH2CH2TeCH2CH2NHCH(CH3)C6H4 -2-OH (L4), respectively, which have 1 or 2 chiral centers. The 1H and 13C NMR spectra of L1 to L4 were found to be characteristic. Treatment of L1 with [Ru(p -cymene)Cl2]2 resulted in [Ru(p -cymene)(4-MeOC6H4TeCH2CH2NH2)Cl]Cl·H2O (1) whereas in the reaction of L2 with [Ru(p -cymene)Cl2]2, the p -cymene ligand is lost resulting in [RuCl(L2 -H)] (4). The reactions of L1, L3 and L4 with HgBr2 resulted in complexes of the type [HgBr2·(L)2] while Na2PdCl4 reacted with L1 to give [PdCl(L1 -H)]. The solid-state structures of L1, L3, 1 and 4 were determined by single-crystal X-ray diffraction studies. The very swift formation of the tellurated amine from a tellurated Schiff base (L1) by hydrolysis has been observed for the first time and has resulted in 1. The Ru,N and Ru,Te bond lengths in 1 are 2.142(3) and 2.6371 (4) Å, respectively. The replacement of the p -cymene ligand with a hybrid organotellurium ligand (L2 -H), resulting in 4, is also a first example of its kind. The Ru center in 4 has a square-planar geometry, with the Ru,N, Ru,Te, Ru,O and Ru,Cl bond lengths being 2.041(6), 2.4983(8), 2.058(5) and 2.308(2) Å, respectively. In the crystals of 4 there are secondary intermolecular Te···Cl interactions and intermolecular N,H···O hydrogen bonds. This is the first example in which coordinated Te in a complex is engaged in two intermolecular secondary interactions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Synthesis, Crystal Structure, and Photoluminescent Properties of a Tetracarbonyl(naphthyridylcarbamoyl)rhenium(I) Complex and a Highly Emissive Tetracarbonyl(naphthyridylamido)rhenium(I) ComplexEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2003Jing-Lin Zuo Abstract The reactions of Re(CO)5X (X = Cl, Br) with 7-amino-2,4-dimethyl-1,8-naphthyridine (H2L1) and 7-[2-(6-chloropyridyl)amino]-2,4-dimethyl-1,8-naphthyridine (HL2) in the presence of tBuOK afforded the ,1 -naphthyridylcarbamoyl complex [Re(CO)4(HL1CO)] (1) and the naphthyridylamido complex [Re(CO)4(L2)] (2), respectively. The structures of HL2, 1·CHCl3, 1·HL3·2CH2Cl2 [HL3 = (7-chloronaphthyridyl)(5,7-dimethylnaphthyridyl)amine], and 2 have been determined by X-ray crystallography. Complex 1 displays a weak emission at 453 nm in an EtOH/MeOH (1:4, v/v) glassy solution at 77 K; complex 2 exhibits an intense (quantum yield: 0.22 in CH2Cl2) and long-lived emission (46 ,s in CH2Cl2), with a solvent-sensitive ,max, in degassed solutions at room temperature. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2003) [source] | ||||||||||||||||||||||||||||||||||||||||||||||