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CoII
Terms modified by CoII Selected AbstractsPhylogeny of Rhus gall aphids (Hemiptera : Pemphigidae) based on combined molecular analysis of nuclear EF1, and mitochondrial COII genesENTOMOLOGICAL SCIENCE, Issue 3 2010Zi-xiang YANG Abstract Rhus gall aphids (Fordinae : Melaphidini) have a disjunct distribution in East Asia and North America and have specific host plant relationships. Some of them are of economic importance and all species form sealed galls which show great variation in shape, size, structure, and galling-site. We present a phylogeny incorporating ten species and four subspecies of Rhus gall aphids based on 1694 base pairs of nuclear elongation factor-1, (EF1,) and mitochondrial cytochrome oxidase subunit II (COII) DNA sequence data. The results suggest that Melaphidini is monophyletic and at the genus level, Schlechtendalia, Nurudea, and Floraphis were each monophyletic. Kaburagia and Meitanaphis were not monophyletic and therefore inconsistent with the current classification. The North American sumac gall aphid, Melaphis rhois, was most closely related to the East Asian Floraphis species, although this was poorly supported. The conservation of gall morphology with respect to aphid phylogeny rather than their host plants suggests that gall morphology is largely determined by the aphids. While there is no evidence of strict co-speciation between the aphids and their primary host plants, switching between recently diverged host plants may be involved in the speciation process in Melaphidini. [source] Identification of economically important Liriomyza species by PCR-RFLP analysis,EPPO BULLETIN, Issue 1 2005L. F. F. Kox Only adult males of Liriomyza bryoniae, L. huidobrensis, L. sativae and L. trifolii can be identified with certainty on basis of their genitalia. Female adults, pupae and larvae can only be identified on the level of groups of species (L. bryoniae and L. huidobrensis vs. L. sativae and L. trifolii). Species identification in all developmental stages is possible using molecular biological techniques. Our method is a PCR amplification of a 790-bp fragment of mitochondrial cytochrome oxidase II (COII) DNA followed by RFLP analysis. The method was tested on single larvae, pupae and adults and proved to be applicable to these three life stages. The specificity of the assay was assessed by comparing the results of the PCR-RFLP analysis with those of morphological analysis using 60 Liriomyza specimens. Molecular and morphological identification agreed for all specimens analysed. PCR-RFLP is a powerful diagnostic tool for rapid and reliable identification of all life stages of economically important Liriomyza species. [source] Selection of evolutionary models for phylogenetic hypothesis testing using parametric methodsJOURNAL OF EVOLUTIONARY BIOLOGY, Issue 4 2001B. C. Emerson Recent molecular studies have incorporated the parametric bootstrap method to test a priori hypotheses when the results of molecular based phylogenies are in conflict with these hypotheses. The parametric bootstrap requires the specification of a particular substitutional model, the parameters of which will be used to generate simulated, replicate DNA sequence data sets. It has been both suggested that, (a) the method appears robust to changes in the model of evolution, and alternatively that, (b) as realistic model of DNA substitution as possible should be used to avoid false rejection of a null hypothesis. Here we empirically evaluate the effect of suboptimal substitution models when testing hypotheses of monophyly with the parametric bootstrap using data sets of mtDNA cytochrome oxidase I and II (COI and COII) sequences for Macaronesian Calathus beetles, and mitochondrial 16S rDNA and nuclear ITS2 sequences for European Timarcha beetles. Whether a particular hypothesis of monophyly is rejected or accepted appears to be highly dependent on whether the nucleotide substitution model being used is optimal. It appears that a parameter rich model is either equally or less likely to reject a hypothesis of monophyly where the optimal model is unknown. A comparison of the performance of the Kishino,Hasegawa (KH) test shows it is not as severely affected by the use of suboptimal models, and overall it appears to be a less conservative method with a higher rate of failure to reject null hypotheses. [source] Distribution and population genetic structure of the Mediterranean pine shoot beetle Tomicus destruens in the Iberian Peninsula and Southern FranceAGRICULTURAL AND FOREST ENTOMOLOGY, Issue 2 2006Teresa Vasconcelos Abstract 1,The Mediterranean pine shoot beetle Tomicus destruens has long been indistinguishable from its congeneric Tomicus piniperda. Both species attack pines, and can be found in sympatry. The geographical distribution of T. destruens is still unclear in most of the Mediterranean Basin. 2,We aimed to describe the geographical distribution and zones of sympatry of both species in the Iberian Peninsula and France, and to study the molecular phylogeographical pattern of T. destruens. 3,Tomicus spp. adults were sampled in Portugal, Spain and France, and a portion of the mitochondrial genes COI and COII was sequenced for 84 individuals. Sequences were aligned to a data set previously obtained from French localities. 4,Tomicus destruens was found in all populations, except for one locality in Portugal and in the Landes (France). It was in sympatry with T. piniperda in two locations on Pinus pinaster and one location on Pinus radiata. 5,Within-population genetic diversity was high, but we found a significant pattern of spatial distribution of genetic variation, as well as a significant effect of the host tree. 6,The data suggest the existence of two glacial refugia, from which T. destruens recolonized its current range. One refugium was located in Portugal where the beetle probably evolved on P. pinaster. The corresponding haplotypes show a West,East frequency gradient. The other refugium was probably in the eastern range, where the beetles evolved on Pinus halepensis and P. pinea. The corresponding haplotypes show an East,West frequency gradient. [source] Differentiation of golden-ringed dragonfly Anotogaster sieboldii (Selys, 1854) (Cordulegastridae: Odonata) in the insular East Asia revealed by the mitochondrial gene genealogy with taxonomic implicationsJOURNAL OF ZOOLOGICAL SYSTEMATICS AND EVOLUTIONARY RESEARCH, Issue 2 2008T. Kiyoshi Abstract Molecular phylogeographical analyses of Anotogaster sieboldii (Selys, 1854) were conducted to reveal the differentiation process of insular populations. The gene genealogy based on 845 bp of the mitochondrial genes (cytochrome oxidase subunit I and subunit II) indicated that A. sieboldii includes two deeply separated lineages. These two major lineages seem to have differentiated in Miocene before the formation of the insular East Asia. One lineage includes three inner clades that correspond to the populations of northern area (the Japanese main islands, Korean Peninsula, Yakushima), Amamioshima and Okinawajima. Populations of Central Ryukyu, including Amamioshima and Okinawajima, might have been divided from the northern populations in early Pleistocene. The other major lineage includes populations of the Yaeyama Group, Taiwan and East China. The former two populations were reconstructed as a reciprocal monophyletic group. Populations of Taiwan and Yaeyama Groups would have been separated from the continental ones in Pleistocene. These two highly divergent lineages should be recognized as distinct species. Furthermore, the mitochondrial lineages revealed six genetically distinct and geographically isolated assemblages: (1) northern populations, (2) Amamioshima, (3) Okinawajima, (4) Yaeyama Group, (5) Taiwan and (6) East China. Zusammenfassung An der Libelle Anotogaster sieboldii wurden molekulare phylogeographische Analysen durchgeführt, um ihre Differenzierungen in Insel-Populationen zu erkennen. Die Gen-Genealogie (basierend auf 845 bp mitochondrialer Gene (COI und COII) zeigte, dass A. sieboldii zwei weit getrennte Abstammungslinien enthält, die sich wahrscheinlich im Miozän vor der Bildung der ostasiatischen Inselwelt differenzierten. Eine Abstammungslinie schließt drei Gruppierungen ein, die den Populationen in den nördlichen Gebieten entsprechen: die japanischen Hauptinseln, die koreanische Halbinsel Yakushima, Amamioshima sowie Okinawajima. Die Populationen von Zentral-Ryukyu, einschließlich Amamioshima und Okinawajima, ist möglicherweise im frühen Pleistozän von den nördlichen Populationen getrennt worden. Die andere größere Abstammungslinie schließt die Populationen der Yaeyama-Gruppe, Taiwan und das Östliche China ein. Zwei dieser Populationen wurden als Teil einer entsprechenden monophyletischen Gruppe rekonstruiert; die Populationen von Taiwan und die Yaeyama-Gruppe sind danach im Pleistozän von den kontinentalen Populationen getrennt worden. Diese zwei sehr differierenden Abstammungslinien sollten als verschiedene Spezies betrachtet werden. Weiterhin werden sechs genetisch verschiedene und geographisch isolierte Gruppierungen deutlich: (1) die nördlichen Populationen, (2) Amamioshima, (3) Okinawajima, (4) die Yaeyama-Gruppe, (5) Taiwan und (6) die Population im östlichen China. [source] Geological barriers and restricted gene flow in the holarctic skipper Hesperia comma (Hesperiidae)MOLECULAR ECOLOGY, Issue 11 2004M. L. FORISTER Abstract Patterns of genetic variation within a species may be a consequence of historical factors, such as past fragmentation, as well as current barriers to gene flow. Using sequence data from the mitochondrial cytochrome oxidase subunit II region (COII) and the nuclear gene wingless, we conducted a phylogeographical study of the holarctic skipper Hesperia comma to elucidate patterns of genetic diversity and to infer historical and contemporary processes maintaining genetic variation. One hundred and fifty-one individuals were sampled from throughout North America and Eurasia, focusing on California and adjacent regions in the western United States where morphological diversity is highest compared to the rest of the range. Analyses of sequence data obtained from both genes revealed a well-supported division between the Old and New World. Within western North America, wingless shows little geographical structure, while a hierarchical analysis of genetic diversity of COII sequences indicates three major clades: a western clade in Oregon and Northern California, an eastern clade including the Great Basin, Rocky Mountains and British Columbia, and a third clade in southern California. The Sierra Nevada and the Transverse Ranges appear to be the major barriers to gene flow for H. comma in the western United States. Relatively reduced haplotype diversity in Eurasia compared to North America suggests that populations on the two continents have been affected by different historical processes. [source] Patterns of population subdivision and gene flow in the ant Nothomyrmecia macrops reflected in microsatellite and mitochondrial DNA markersMOLECULAR ECOLOGY, Issue 9 2003M. Sanetra Abstract The Australian endemic ant Nothomyrmecia macrops is renowned for having retained a large proportion of ,primitive' morphological and behavioural characters. Another less studied peculiarity of this species is the production of short-winged (brachypterous) female sexuals, which presumably are poor dispersers. The males, in contrast, bear a full set of normally developed wings and thus may disperse widely. We investigated patterns of genetic differentiation within and among three distantly separated populations in South Australia using nine polymorphic microsatellite loci and four regions of mitochondrial DNA (COI, COII, Cytb, lrRNA). We sampled eight subpopulations, one in the Lake Gilles CP, two near Penong and five around Poochera where distances ranged from 360 km to sites separated by 2,10 km. Only little differentiation was found at the local scale (within the assumed dispersal distance of males) using nuclear markers, whereas the three distant locations were moderately differentiated (FST = 0.06). Mitochondrial DNA genetic structure was much more pronounced on all scales (,ST = 0.98), with regular differences in both haplotype composition and frequency even occurring among closely located sites. This lack of congruence between nuclear and mitochondrial markers strongly suggests limited female dispersal and male-biased gene flow among populations. As to the conservation status of the species there is no evidence for severe population reductions in the recent past, which would have left populations genetically depauperate. [source] Atelinae phylogenetic relationships: The trichotomy revived?AMERICAN JOURNAL OF PHYSICAL ANTHROPOLOGY, Issue 4 2004A.C. Collins Abstract This research examines phylogenetic relationships between members of the Atelinae subfamily (Alouatta, Ateles, Brachyteles, and Lagothrix), based on analysis of three genetic regions. Two loci, cytochrome c oxidase subunit II (COII) and the hypervariable I portion of the control region, are part of the mitochondrial genome. The other is a single-copy nuclear gene, Aldolase A Intron V. Analysis of these genetic regions provides support for tribe Alouattini containing the Alouatta species, while tribe Atelini contains the other three genera. However, these three genetic regions produce conflicting results for relationships among tribe Atelini members. Previous genetic studies supported grouping Brachyteles with Lagothrix, leaving Ateles in a separate subclade. The present data sets vary based on the genetic region analyzed and method of analysis suggesting all possible cladistic relationships. These results are more consistent with investigations of morphology and behavior among these primates. The primary cause of discrepancy between this study and previous genetic studies is postulated to reside in increased sampling in the present study of genetic variation among members of the Atelinae, specifically Ateles. The present study utilized samples of Ateles from all postulated species for this genetically variable primate, while previous studies used only one or two species of Ateles. This paper demonstrates that shifting relationships are produced when different species of Ateles are used to reconstruct phylogenies. This research concludes that a trichotomy should still be supported between members of tribe Atelini until further analyses, which include additional Atelinae haplotypes are conducted. Am J Phys Anthropol, 2003. © 2003 Wiley-Liss, Inc. [source] Phylogeography of the Iberian populations of Mioscirtus wagneri (Orthoptera: Acrididae), a specialized grasshopper inhabiting highly fragmented hypersaline environmentsBIOLOGICAL JOURNAL OF THE LINNEAN SOCIETY, Issue 3 2009JOAQUÍN ORTEGO Phylogeographic studies from western Palaearctic have generally focused on species able to disperse and track their emerging suitable habitats after the last ice age. However, data on species whose biogeographical histories differ from this bulk of Palaearctic fauna are scarce. This is clearly the case of some specialized organisms inhabiting inland hypersaline environments, which are likely to have had a wider distribution range during the late Tertiary and may have persisted through the Pleistocene to the present day only constituting relict populations. In this study, we use partial sequences from two mitochondrial genes [16S rRNA (16S) and cytochrome oxidase subunit II (COII)] to investigate the phylogeography of the Iberian populations of Mioscirtus wagneri (Orthoptera: Acrididae), a specialized grasshopper exclusively inhabiting hypersaline low grounds. Our results show that M. wagneri exhibits a marked phylogeographical structure, forming three main clades which correspond with populations located in north-east, central,south-east and south-west Iberia. These geographical areas did not share any haplotype, indicating that gene flow between them is absent. Nested clade analyses revealed that these lineages have probably evolved in allopatry and data on sequence divergence suggest population fragmentation from the Early Pleistocene. Overall, these results provide a broader perspective on the contribution of historical climate/geological events to biogeographical patterns of organisms currently forming relict populations of great conservation concern. © 2009 The Linnean Society of London, Biological Journal of the Linnean Society, 2009, 97, 623,633. [source] Phylogeny, biogeography and the stepwise evolutionary colonization of intertidal habitat in the Liparocephalini based on morphological and molecular characters (Coleoptera: Staphylinidae: Aleocharinae)CLADISTICS, Issue 4 2010Kee-Jeong Ahn A phylogenetic analysis of the tribe Liparocephalini Fenyes is presented based on morphological and molecular characters. The data set comprised 50 adult morphological characters, partial COI (907 bp), COII (366 bp) and 12S rDNA (325,355 bp), and nearly complete sequences of 18S rDNA (1768,1902 bp) for 21 species. Eighteen species of liparocephaline beetles from all eight genera and three outgroups, are included. The sequences were analysed separately and simultaneously with morphological characters by direct optimization in the program POY4 and by partitioned Bayesian analysis for the combined data. The direct optimization (DO) tree for the combined data under equal weighting, which also shows a minimum incongruence length difference value, resulted in a monophyletic Liparocephalini with the following patterns of phylogenetic relationships (outgroup ((Baeostethus, Ianmoorea) (Paramblopusa ((Amblopusa, Halorhadinus) (Liparocephalus, Diaulota))))). A sensitivity analysis using 16 different parameter sets for the combined data shows the monophyly of the liparocephalines and all its genera under all parameter sets. Bayesian analysis resulted in topological differences in comparison with the DO tree under equal weighting only in the position of the genus Paramblopusa and clade (Amblopusa + Halorhadinus), which were reversed. Historical biogeography and the stepwise evolutionary colonization of intertidal habitat in the Liparocephalini are discussed. Based on the biogeographical analyses, we hypothesize that the ancestor of the Liparocephalini occurred along the Panthallassan Ocean, the direct antecedent of the Pacific Ocean, followed by repeated dispersals to the Nearctic from the Palearctic. We also hypothesize that ancestors of the Liparocephalini appear to have arisen in the littoral zone of beaches and then colonized rocky reef areas in the low tidal zone later through high- to mid-tide zones. ,© The Willi Hennig Society 2009. [source] Humidity-Sensitive Magnet Composed of a Cyano-Bridged CoII,NbIV Dimetallic AssemblyEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 26 2010Kenta Imoto Abstract Nanoporous magnetic materials composed of metal-assembled complexes are expected to exhibit chemical sensitivity. In this work, we observed a humidity-induced reversible change between ferromagnetism and antiferromagnetism in a new type of a cobalt octacyanoniobate based magnet in the high-humidity region. This humidity response is caused by the adsorption and desorption of non-coordinated water (so-called zeolitic water) molecules in the interstitial site. Such a phenomenon is achieved by the structural flexibility of an octacyanometalate-based magnet. [source] Pillared Layered Metal Phosphonates Showing Field-Induced Magnetic TransitionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 6 2010Peng-Fei Wang Abstract The first examples of metal phosphonates based on 6-phosphononicotinic acid (pnaH3), namely, M3(pna)2(H2O)2 {1: M = CuII, 2: M = CoII} are reported. Both possess pillared layered structures. Within the inorganic layer, chains made up of dimers of edge-sharing {M2O6} octahedra and {M1O6} octahedra through O(1W), O,P,O, and O,C,O units are interconnected by {PO3C} tetrahedra. The pyridyl groups of pna3, serve as the pillars. An antiferromagnetic ground state is found for each compound. When the external field reaches critical points at low temperature, compound 1 features a spin flop transition, whereas 2 shows metamagnetic behavior. [source] Oxido Pincer Ligands , Exploring the Coordination Chemistry of Bis(hydroxymethyl)pyridine Ligands for the Late Transition MetalsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2009Axel Klein Abstract Coordination of the 2,6-bis(hydroxymethyl)pyridine-based oxido pincer ligands RR,pydimH2 [R = R, = H (pydimH2); R = R, = Me (pydipH2); R = 2-tolyl, R, = Me (pydotH2)] towards late transition metals CoII, NiII, CuII, ZnII, PdII and PtII allows the formation of molecular species (complexes), which exhibit three main structural motifs in the solid state. The two main species are pentacoordinate [(RR,pydimH2)MCl2] and hexacoordinate [(RR,pydimH2)2M]X2, both of which are stable in solution and can be interconverted by changing the solvent polarity. The disproportionation equilibrium [(RR,pydimH2)MCl2] [rlhar2] [(RR,pydimH2)2M]2+ + [MCl4]2, was studied by optical spectroscopy. The chiral ligand pydotH2 allows the formation of chiral complexes. In the square-planar complexes [(pydimH2)2MCl2] (M = PdII or PtII) the oxido donor functions of the ligands do not take part in the coordination.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Synthesis, Structural, Thermal and Magnetic Characterization of a Pyrophosphato-Bridged Cobalt(II) ComplexEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 17 2008Oluwatayo F. Ikotun Abstract The reaction in water of CoII sulfate heptahydrate with 1,10-phenanthroline (phen) and sodium pyrophosphate (Na4P2O7) in a 2:4:1 stoichiometric ratio resulted in the crystallization of a neutral dinuclear CoII complex, {[Co(phen)2]2(,-P2O7)}·6MeOH (1), as revealed by a single-crystal X-ray diffraction study. The bridging pyrophosphato ligand between the two [Co(phen)2]2+ units in a bis(bidentate) coordination mode places the adjacent metal centers at 4.857 Å distance, and its conformation gives rise to intramolecular ,,, stacking interaction between adjacent phen ligands. Indeed, intermolecular ,,, stacking interactions between phen ligands from adjacent dinuclear complexes create a supramolecular 2D network in 1. Magnetic susceptibility measurements on a polycrystalline sample of 1 in the temperature range 1.9,295 K are typical of an overall antiferromagnetic coupling with a maximum of the magnetic susceptibility at 3.0 K. The analysis of the magnetic data in the whole temperature range allows the determination of the value of the intramolecular magnetic coupling (J = ,1.23 cm,1). The ability of the pyrophosphato ligand to mediate magnetic interactions between different first-row transition-metal ions when adopting the bis(bidentate) bridging mode is analyzed and discussed in the light of the small number of magneto-structural reports on this type of compound, bearing in mind the number of unpaired electrons and type of magnetic orbitals on each metal center. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Tetrahedral CoII Complexes with CoI2O2 and CoO2S2 Cores , Crystal Structures of [Co{HN(OPPh2)(SPPh2)- O}2I2] and [Co{N(OPPh2)(SPPh2)- O,S}2]EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 29 2007M. Carla Aragoni Abstract The compound [CoII{HN(OPPh2)(SPPh2)- O}2I2] (1) was synthesised by the reaction of cobalt in powder with the iodine adduct of tetraphenylthiooxoimidodiphosphinic acid, HN(OPPh2)(SPPh2), in Et2O; treatment of compound 1 with NaOH resulted in deprotonation of the ligands bound to the metal ion and a separation of [CoII{N(OPPh2)(SPPh2)- O,S}2] (2). Molecular structures of complexes 1 and 2 were elucidated by X-ray diffraction analysis, which revealed a CoI2O2 tetrahedral core for compound 1 in which two neutral ligands bind through the oxygen atoms the CoII ion, and a tetrahedral CoO2S2 core for compound 2 with the oxygen and sulfur atoms of each anionic ligand chelating a CoII centre. Variable-temperature magnetic susceptibility measurements are consistent with tetrahedral high-spin (S = 3/2) CoII that possesses a 4A2 ground state with best fit parameters g = 2.25, |D| = 12.0 cm,1 and g = 2.37, |D| = 11.9 cm,1 for complexes 1 and 2, respectively. The compounds were further characterised by UV/Vis and IR spectroscopy. DFT calculations were performed on model complexes [CoII{N(OPH2)(SPH2)- O,S}2] (3) and [CoII{N(SPH2)2 - S,S,}2] (4) to compare the electronic properties of the CoO2S2 and CoS4 cores. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Transition-Metal (MnII and CoII) Complexes with the Heteropolymolybdate Fragment [AsVMo9O33]7,: Crystal Structures, Electrochemical and Magnetic PropertiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 17 2007Yanyan Yang Abstract Two novel heteropolymolybdates, [(CH3)4N]8n[M(H2O)5]2n(H3O)2n[{M(H2O)5}2(MAsVMo9O33)2]n[M(H2O)4(MAsVMo9O33)2]n·20nH2O (M = Mn2+, 1; M = Co2+, 2), constructed from the new fragment (AsVMo9O33)7, and a transition metal have been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, and single-crystal X-ray diffraction. Structurally the title complexes resemble a sandwich-type complex because they involve the coordination of two transition metals to two [AsVMo9O33]7, fragments, which derive from the well-known B -, - Keggin structure. Compounds 1 and 2 exhibit a one-dimensional chain-like framework [M(H2O)4(MAsVMo9O33)2]8n, with isolated {[M(H2O)5]2(MAsVMo9O33)2}6, units residing among the chains. The magnetic properties of the two complexes were investigated to indicate typical antiferromagnetic interactions through the MnII,O,MnII bridge unit for complex 1 and the CoII,O,CoII bridge unit for complex 2. (© 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] Synthesis, Complexation and Spectrofluorometric Studies of a New NS3 Anthracene-Containing Macrocyclic LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2006Abel Tamayo Abstract A new fluorescent device for detecting protons and metal ions, 11-(9-anthracenylmethyl)-1,4,7-trithia-11-azacyclotetradecane (L), has been synthesised. In addition, the photophysical properties of both the free and protonated species have been examined by absorption and fluorescence titrations of dichloromethane solutions of L with methanesulfonic acid. The coordinating properties of L toward PdII, ZnII, NiII and CoII have been studied both in solution and in the solid state. Different behaviours have been observed in the absorption and fluorescence titrations of L with the above-mentioned transition-metal ions. To evaluate whether these differences were due to the existence of equilibria between protonated and complexed species, such titrations have been repeated in the presence of an equivalent amount of acid. The structure of the [Pd(L)](BF4)2 complex has been solved by X-ray crystallography. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Highly Symmetrical Tetranuclear Cluster Complexes Supported by p - tert -Butylsulfonylcalix[4]arene as a Cluster-Forming LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2006Takashi Kajiwara Abstract Square-planar tetranuclear clusters [M4(L)(AcO)4(,4 -OH)], (M = MnII, CoII, and NiII) are synthesized using tetra-anionic p - tert -butylsulfonylcalix[4]arene (L4,) as a cluster-forming ligand. Three complexes are crystallographically isostructural, being crystallized in the triclinic crystal system with space group P. The calix[4]arene acts as a tetrakis fac -tridentate ligand through four phenoxo and four sulfonyl oxygen atoms to form square arrangement of four metal ions, which are further bridged by four chelating acetate ions and one hydroxo ion in a ,4 manner to complete the hexacoordination of each metal center. Although the whole molecule of each complex is crystallographically independent, the molecule is highly symmetrical with a pseudo-four-fold axis lying on the ,4 -OH, group. The tetranuclear clusters are stable enough to maintain the core structures even in highly dilute solution (,10 ,M), which was confirmed by mass spectroscopic study, however, bridging acetates were easily exchanged by other carboxylate chelates to form derivatives such as [M4(L)(BzO)4(OH)],. Metal,metal interactions were investigated by means of magnetic susceptibility, and it was revealed that both ferro- and antiferromagnetic interactions occur in the NiII complex depending on the bridging angles of Ni,O,Ni. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Self-Assembly of a Tetranuclear CoIII -Metallacycle from the Reaction of a Bis(benzene- o -dithiolato) Ligand with CoII and Subsequent Aerial OxidationEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 3 2006F. Ekkehardt Hahn Abstract The bis(benzene- o -dithiol) ligand [(HS)2 -2,3-C6H3,CH2,C6H3 -2,3-(SH)2] (H4 - 1) reacts, after deprotonation with Li2CO3, with CoCl2·6H2O. Aerial oxidation in methanol gives the tetranuclear metallacycle Li4[Co4(1)4]. The X-ray structure analysis of (PNP)4[Co4(1)4] (7) reveals a cyclic structure in which each of the bis(benzene- o -dithiolato) ligands forms a bridge between two cobalt centers. Two differently coordinated cobalt atoms (syn and anti) are observed in the tetranuclear complex. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] N -Methylation Effects on the Coordination Chemistry of Cyclic Triamines with Divalent Transition Metals and Their CoII Dioxygen CarriersEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2006Silvia Del Piero Abstract The thermodynamics of complex formation of CoII and CdII ions with the triaza macrocyclic ligand 1,4,7-triazacyclononane (tacn) and its N -methylated derivative 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3tacn) has been studied in dimethyl sulfoxide (DMSO) at 298.1 K and in an ionic medium (0.1 M Et4NClO4) by means of potentiometric, UV/Vis, calorimetric and FT-IR techniques. The results are discussed by taking into account electronic and steric effects as well as solvation of the species concerned. Computational methods based on density functional theory (DFT) have been used to obtain structural information about the ligands and their complexes in order to provide further, independent insights into the effect of N -methylation on the coordination affinity of the ligands towards the metal ions. The computational suggestions are of great help to correlate steric effects and thermodynamic results. The kinetics of dioxygen uptake for the formation of the Co(tacn)2O2 superoxo adduct has also been studied by means of UV/Vis measurements. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] A Crystalline Phase Transition and Optical Properties in a CoIICuII Oxamato-Bridged Ferrimagnetic ChainEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 24 2005Cynthia L. M. Pereira Abstract The compound [CoCu(opba)(DMSO)3] (1) [opba = ortho -phenylenebis(oxamato)] has been synthesized and characterized. Its crystal structure has been analyzed by X-ray diffraction techniques at 100 and 298 K. A structural phase-transition has been detected at around 150 K. An orthorhombic crystalline system is found at both temperatures, with very similar unit-cell dimensions. At room temperature 1 crystallizes in the Pnam space group (, -1 phase), with a = 7.6712(2), b = 14.8003(3), c = 21.0028(5) Å, and Z = 4, whereas at low temperature it crystallizes in the Pna21 space group (, -1 phase), with a = 7.3530(2), b = 14.5928(4), c = 21.0510(7) Å, and Z = 4. Both crystalline phases consist of linearly ordered bimetallic chains with the [Cu(opba)]2, units tied by CoII ions to form a one-dimensional system. The DMSO molecules in , -1, which are coordinated to either CuII or CoII, are disordered. At low temperature, a small reorganization of the CuII and CoII environments is observed. The origin of this phase transition, which is completely reversible, is the modification of the crystalline packing with the temperature. Linear birefringence measurements were done on single crystals in the 100,300 K temperature range. Around 150 K, the linear birefringence curve shows an inflexion that is interpreted as being related to the conversion of ,-1 into , -1. Both dc and ac magnetic measurements were performed on the polycrystalline sample. The results reveal a one-dimensional ferrimagnetic behavior. Single crystal optical characterization at room temperature shows that 1 presents a very strong dichroism superposed on the linear birefringence. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Electronic Interactions in Ferrocene- and Ruthenocene-Functionalized Tetraazamacrcocyclic Ligand Complexes of FeII/III, CoII, NiII, CuII and ZnIIEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2005Peter Comba Abstract The syntheses of ferrocene- and ruthenocene-functionalized tetraazamacrocyclic ligands and their corresponding transition metal complexes are described. Reaction of N,N, -bis(2-aminoethyl)-1,3-propanediamine (2,3,2-tet) with 1,1,-diformylferrocene and 1,1,-diformylruthenocene produces the ligands fcmac and rcmac in 81,85% yield. Examination of their CuII, NiII, CoII, ZnII and FeII/III complexes by IR, UV/Vis, EPR and Mössbauer spectroscopy as well as by electrochemical studies suggests electronic communication between the two metal centers of each complex. The molecular structure of [CuII(fcmac)(FBF3)]BF4, determined by X-ray structure analysis, is reported and shows that the distance between the two metals is 4.54 Å. Stability constants, determined by potentiometric titration, indicate that the copper(II) complexes are of similar stability as those with unfunctionalized tetraazamacrocyclic ligands (e.g. cyclam = 1,4,8,11-tetraazacyclotetradecane); stability constants of cobalt(II) complexes are about 2 log units smaller, those of nickel(II) and zinc(II) complexes are reduced by more than 10 log units. This selectivity is discussed on the basis of the structural studies. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Funnel Complexes with CoII and NiII: New Probes into the Biomimetic Coordination Ability of the Calix[6]arene-Based Tris(imidazole) SystemEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2004Olivier Sénèque Abstract The coordination properties of the calix[6]arene-based tris(imidazole) ligand X6Me3Imme3 were further explored with CoII and NiII. This imidazole system stabilizes tetrahedral mononuclear CoII complexes with an exchangeable fourth exogenous ligand (water, alcohol, amide) located at the heart of the hydrophobic calixarene cavity. With a weak donor ligand such as a nitrile, both four-coordinate tetrahedral and five-coordinate trigonal bipyramidal complexes were obtained. The latter contains a second nitrile molecule trans to the included guest nitrile. These complexes were characterized in solution as well as in the solid state. The NiII complexes are square-based pyramidal five-coordinate edifices with a guest nitrile inside the cavity and a water molecule outside. A comparison with previously described ZnII and CuII complexes emphasizes the flexibility of this ligand. A comparison with carbonic anhydrase, a mononuclear zinc enzyme with a tris(histidine) coordination core, shows that X6Me3Imme3 displays many structural features of this enzyme except for the cis coordination of the exogenous ligands. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Synthesis, Characterization and Electrochemistry of the Novel Dawson-Type Tungstophosphate [H4PW18O62]7, and First Transition Metal Ions DerivativesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2004Israel-Martyr Mbomekalle Abstract Following the synthesis of pure [H4PW18O62]7, (PW18), its derivatives monosubstituted with M (M = MoVI, VIV, VV, MnII, FeIII, CoII, NiII CuII and ZnII) were obtained. All compounds were characterized by elemental analysis, IR, UV/visible and 31P NMR spectroscopy. Their cyclic voltammetry properties were studied as a function of pH and systematically compared with those of their analogs derived from the symmetrical species, [P2W18O62]6,(P2W18). Comparison of the two unsubstituted precursors revealed that the merging of the first two waves of the monophosphate occurred in a less acidic medium than for the diphosphate. The observations point to the higher basicity of the reduced forms of PW18 compared with those of P2W18. The fingerprint pattern observed for ,2 -P2W17M derivatives in media of pH = 3 consisted of the splitting of the third W redox system into two one-electron closely spaced waves which is in contrast to the same system in ,1 -P2W17M. This peculiarity was also obtained for several of the present ,2 -PW17M systems in media of pH = 3 and confirmed that ,2 -substituted derivatives were indeed formed. The absence of this peculiar behavior in some other derivatives is consistent with smooth variations of acid-base properties from one derivative to the next. The electrocatalytic properties of all the compounds are illustrated by the reduction of nitrite by reduced PW18 and of nitrate by reduced ,2 -PW17Cu. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Resolution of Racemic N -Benzyl ,-Amino Acids by Liquid-Liquid Extraction: A Practical Method Using a Lipophilic Chiral Cobalt(III) Salen Complex and Mechanistic StudiesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 7 2008Pawel Dzygiel Abstract The efficient resolution of racemic N -benzyl ,-amino acids (N -Bn-AA) has been achieved by a liquid-liquid extraction process using the lipophilic chiral salen,cobalt(III) complex [CoIII(3)(OAc)]. As a result of the resolution by extraction, one enantiomer (S) of the N -benzyl ,-amino acid predominated in the aqueous phase, while the other enantiomer (R) was driven into the organic phase by complexation to cobalt. The complexed amino acid (R) was then quantitatively released by a reductive (CoIII,,,CoII) counter-extraction with aqueous sodium dithionite or L -ascorbic acid in methanol. Thereductive cleavage allowed to recover the [CoII(3)] complex in good yield, which could be easily re-oxidized to[CoIII(3)(OAc)] with air/AcOH and reused with essentially no loss of reactivity and selectivity. Investigation on the nitrogen substitution indicates that the presence of a single benzyl group on the amino acid nitrogen is important to obtain high enantioselectivity in the extraction process. The kinetic vs. thermodynamic nature of the resolution process was also investigated with an enantiomeric exchange experiment, which shows that the liquid-liquid extraction with [CoIII(3)(OAc)] is an equilibrium process operating under thermodynamic control. In the absence of a suitable crystal structure of the [CoIII(3)(N -Bn-AA)] complexes, computational and spectroscopic studies were used to investigate how the N -benzyl ,-amino acids are accommodated in the "binding pocket" of the chiral cobalt complex. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Organic Ligands Made Porous: Magnetic and Catalytic Properties of Transition Metals Coordinated to the Surfaces of Mesoporous OrganosilicaADVANCED FUNCTIONAL MATERIALS, Issue 7 2010Andreas Kuschel Abstract Inorganic solids with porosity on the mesoscale possess a high internal surface area and a well-accessible pore system. Therefore, it is a relevant task to equip the surfaces of such materials with a maximum density of various organic functional groups. Among these functions it is the capability of coordinating to metal species as a ligand that is of extraordinary importance in many areas, for example, in catalysis. This paper describes how prominent ligands containing donor functions such as carboxylic, thio, chelating, or amine groups can be obtained in the form of nanoporous organosilica materials. The coordination of metal centers such as CoII, MnII, VIV, or PtIV is studied in detail. The magnetic properties of the corresponding materials and some applications in catalysis are reported. A quantitative determination of the surface density of donor atoms by distance measurements using EPR spectroscopy is shown. [source] Kinetically Controlled Synthesis of Hexagonally Close-Packed Cobalt Nanorods with High Magnetic CoercivityADVANCED FUNCTIONAL MATERIALS, Issue 12 2009Yaghoub Soumare Abstract High-quality monodisperse metallic cobalt nanorods are obtained by the reduction of carboxylate salts of CoII in 1,2-butanediol using a rapid, simple, and solid-template-free procedure. In this polyol process, particle shape can be controlled via the growth rate, which depends on three parameters: i) the nature of the cobalt carboxylate, ii) the temperature ramp, and iii) the basicity of the medium. Cobalt in the hexagonally close-packed phase favored the growth of anisotropic particles. Magnetic measurements of the cobalt nanorods indicate they are ferromagnetic at room temperature. They have a very high coercivity of 9.0 kOe at 140,K, much higher than that observed for wires prepared with solid templates. This can be attributed to their small mean diameter and high crystallinity. [source] Complexation of late transition metal(II) ions (M,=,Co, Ni, Cu, and Zn) by a macrocyclic thiacrown ether studied by means of electrospray ionization mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 11 2009Nikos G. Tsierkezos Electrospray ionization mass spectrometry (ESI-MS) is used to probe the metal-binding selectivity of a macrocyclic thiacrown ether (C44H32S20) towards CoII, NiII, CuII, and ZnII. In homogeneous 1:1 v/v methanol/dichloromethane solutions, it is found that the thia ligand very selectively binds traces of copper even in the presence of an excess of the other metal ions. The large selectivity is ascribed to the redox-active nature of copper which enables a reduction from CuII to CuI, occurring upon ESI-MS, whereas CoII, NiII and ZnII cannot undergo similar redox reactions. Copyright © 2009 John Wiley & Sons, Ltd. [source] Inverse bilayer structure of mononuclear CoII and NiII complexes of the type M(H2O)3(SO4)(4-CNpy)2ACTA CRYSTALLOGRAPHICA SECTION B, Issue 4 2009Birinchi K. Das Two new metal compounds of the formula [M(H2O)3(SO4)(4-CNpy)2]·H2O [M = Ni (1) and Co (2), 4-CNpy = 4-cyanopyridine] have been prepared and studied by X-ray diffraction. In both of these compounds the 4-CNpy ligands are coordinated via pyridyl-N atoms to the metal ions in a cis fashion. The neutral complexes along with the uncoordinated H2O molecules are glued together preferentially into inverse bilayers by non-covalent interactions, including unique interlayer ,,, interactions between antiparallel nitrile groups. Hartree,Fock and density-functional theory (DFT) calculations indicate that the ,,, interactions are energetically significant. The unit-cell similarity index (,) of 0.0046 for the compounds suggests their isostructurality, which is also supported by their X-ray powder diffraction patterns that can be almost superimposed. [source] | ||||||||||||||||||||||||||||