| 1. |
- Poulsen, R. D., et al.
(författare)
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Effects of Weak Intermolecular Interactions on the Molecular Isomerism of Tricobalt Metal Chains
- 2009
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 1520-5126 .- 0002-7863. ; 131:22, s. 7580-7591
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Tidskriftsartikel (refereegranskat)abstract
- Depending on the number of interstitial solvent molecules, n, crystals of the linear chain compound Co-3(dipyridylamide)(4)Cl-2 center dot nCH(2)Cl(2) adopt either symmetrical or unsymmetrical metal chain structures. We explore here the possible reasons for such behavior using Hirshfeld surface analysis of intermolecular interactions as well as the charge density determined from 100(1) K X-ray diffraction data on the unsymmetrical complex Co-3(dipyridylamide)(4)Cl-2 center dot 2.11CH(2)Cl(2), u-1, and crystal structures of u-1 determined from single crystal synchrotron X-ray diffraction data at 20, 150, and 300 K. The new crystal structures are compared with previous structural results on a crystal with slightly different solvent content. This change in solvent content only affects the bond distances to atom Co(3), which are also strongly affected by temperature changes due to a spin crossover transition. Large differences in intermolecular interactions are revealed by the Hirshfeld surface analysis between symmetrical (s-1) and unsymmetrical (u-1) crystal solvates, suggesting that the molecular isomerism is strongly influenced by crystal packing effects. Topological analysis of the static electron density of u-1 suggests that there is direct metal-metal bonding for both the shorter Co(1)-Co(2) and the longer Co(2)-Co(3) contact. The approximate description of the system as a (Co2)(2+)-dimer and an isolated Co2+-ion is reflected in the character of the metal-ligand interactions, which are more ionic for the isolated Co(3) atom, and the topological charges Co(1)(+0.50), Co(2)(+0.77), and Co(3)(+1.36). The two termini of u-1 are found to be very different, both in terms of structural surroundings as well as topology. The central Co(2) atom is similar to a cobalt atom in a tetragonally distorted octahedral environment resulting in preferred occupancy in the t(2g) orbitals. The Co(1) atom has significant deformation in the xz and yz planes (z along the chain axis, x and y toward ligands) reflecting covalent interactions with the terminal chlorine atom Cl(1). The Co(3) atom has a relatively high occupancy of the d(x2-y2) orbital and a relatively low occupancy of the d(xy) orbital confirming that these orbitals are involved in the spin crossover process and predominantly responsible for the observed variation in bond lengths with temperature.
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| 2. |
- Scherstén, Anders, et al.
(författare)
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Re-Os and U-Pb constraints on gold mineralisation events in the Meso- to Neoarchaean Storo greenstone belt, Storo, southern West Greenland
- 2012
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Ingår i: Precambrian Research. - : Elsevier BV. - 0301-9268. ; 200, s. 149-162
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Tidskriftsartikel (refereegranskat)abstract
- The Storo greenstone belt in Godthabsfjord, southern West Greenland consists of juxtaposed rock units of different age and origin, and hosts gold mineralisation that is associated with arsenopyrite along a contact between lithological units and along the axial plane of a large fold core. The age and origin of the gold is debatable, but in this paper, we present new arsenopyrite Re-Os and zircon U-Pb data to constrain the age of the Storo gold deposit. A 2.71 +/- 0.05 Ga arsenopyrite isochron and 2.707 +/- 0.008 Ga highly radiogenic arsenopyrite from a mineralisation along a rock contact, together with a 2.64 +/- 0.02 Ga arsenopyrite isochron along the axial plane of the fold core indicate a two-stage mineralisation process. While the 2.707 +/- 0.008 Ga highly radiogenic arsenopyrite provides firm support for an early mineralisation event, a mixing origin cannot yet be excluded for the 2.71 +/- 0.05 Ga isochron. The 2.64 +/- 0.02 Ga isochron is in perfect agreement with recent U-Pb zircon data (Nutman et al., 2007. Precambrian Research 159, 19-32) and these data are best explained by orogenic mineralisation during amphibolite facies metamorphism along structural weak planes. The initial Os-187/Os-188 value of 0.56 +/- 0.16 for the 2.64 +/- 0.02 Ga isochron indicates a crustal source for the metals, whereas the initial Os-187/Os-188 = -0.1 +/- 0.6 for the 2.71 +/- 0.05 Ga isochron remains unconstrained. Re-Os data are best explained by relatively short crustal residence times of less than 0.1 Ga, wherein the Os, and associated metals, were extracted from the mantle at a time younger than 2.8 Ga, and in which the 2.64 +/- 0.02 Ga stage formed by mobilisation of an earlier mineralisation. Detrital zircon constraints imply volcanism and sediment deposition for parts of the belt at <= 2.84 Ga and that these units were tectonically juxtaposed to similar to 3.05 Ga rocks within the belt. The units that were deposited <= 2.84 Ga record metamorphic zircon U-Pb ages of similar to 2.63 Ga, but evidence for 2.72 Ga metamorphism, which is ubiquitous in adjacent terranes, is lacking. (C) 2012 Elsevier B.V. All rights reserved.
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