Stabilisation of two Cu(I)-amino N bonds in presence of imino N's

Two structurally characterised examples of air stable Cu-1 (amino N)(2)(imino N)(2) chromophores having a Cu(II/I) potential of 0.01-0.19 V vs SCE in CH2Cl2 are provided using two tetradentate N-donor ligands.

Mixed ligand binuclear copper(I) complexes containing (Cu2N8)-N-I chromophores. Observation of emissions from MLCT excited states involving two different ligands

Using the 1:2 condensate (L) of diethylenetriamine and benzaldehyde as the main ligand, binuclear copper(l) complexes [Cu2L2(4,4'-bipyridine)](CIO4)(2).0.5H(2)O (1a) and [Cu2L2(1,2-bis(4-pyridyl)ethane)](CIO4)(2) (1b) are synthesised. The two metal ions in la are bridged by 4,4'-bipyridine and those in 1b by 1,2-bis(4-pyridyl)ethane, From the X-ray crystal structure of la, each metal ion is found to be bound to three N atoms of L and one of the two N atoms of the bridging ligand in a distorted tetrahedral fashion. The Cu(I)-N bond lengths in la lie in the range of 1.998(5)-2.229(6) Angstrom. Electrochemical studies in dichloromethane (DCM) show that the (Cu2N8)-N-I moieties in la and 1b are composed of two essentially non-interacting (CuN4)-N-I cores with Cu-II/I potential of 0.44 V vs. SCE. While la displays metal induced quenching of the inherent emission of 4,4'-bipyridine in DCM solution, 1b exhibits two weak emission bands in DCM solution at 425 and 477 nm (total quantum yield = 3.59 x 10(-5)) originating from MLCT excited states. With the help of Extended Huckel calculations it is established that the higher energy emission in 1b is from Cu(I) --> bridging-ligand charge transfer excited state and the lower energy one in 1b from Cu(I) --> L charge transfer excited state.

Synthesis, spectroscopy and spectroelectrochemistry of chlorocarbonyl {1,2-bis[(2,6-diisopropylphenyl)imino]-acenaphthene-kappa(2)-N,N '}rhodium (I)

Reaction of the dinuclear complex [{Rh(CO)(2)}(2) (mu-Cl)(2)]with an alpha-diimine ligand, 1,2- bis[(2,6-diisopropylphenyl) imino] acenaphthene (iPr(2)Ph-bian), produces square-planar [RhCl(CO)(iPr(2)Ph-bian)]. For the first time, 2: 1 and 1: 1 alpha-diimine/dimer reactions yielded the same product. The rigidity of iPr(2)Ph-bian together with its flexible electronic properties and steric requirements of the 2,6-diisopropyl substituents on the benzene rings allow rapid closure of a chelate bond and replacement of a CO ligand instead of chloride. A resonance Raman study of [RhCl(CO)(iPr(2)Ph-bian)] has revealed a predominant Rh-to-bian charge transfer (MLCT) character of electronic transitions in the visible spectral region. The stabilisation of [RhCl(CO)(iPr(2)Ph-bian)] in lower oxidation states by the pi-acceptor iPr(2)Ph-bian ligand was investigated in situ by UV-VIS, IR and EPR spectroelectrochemistry at variable temperatures. The construction of the novel UV-VIS-NIR-IR low-temperature OTTLE cell used in these studies is described in the last part of the paper.

Bioclimatic envelope model of climate change impacts on blanket peatland distribution in Great Britain

Blanket peatlands are rain-fed mires that cover the landscape almost regardless of topography. The geographical extent of this type of peatland is highly sensitive to climate. We applied a global process-based bioclimatic envelope model, PeatStash, to predict the distribution of British blanket peatlands. The model captures the present areal extent (Kappa = 0.77) and is highly sensitive to both temperature and precipitation changes. When the model is run using the UKCIP02 climate projections for the time periods 2011–2040, 2041–2070 and 2071–2100, the geographical distribution of blanket peatlands gradually retreats towards the north and the west. In the UKCIP02 high emissions scenario for 2071–2100, the blanket peatland bioclimatic space is ~84% smaller than contemporary conditions (1961–1990); only parts of the west of Scotland remain inside this space. Increasing summer temperature is the main driver of the projected changes in areal extent. Simulations using 7 climate model outputs resulted in generally similar patterns of declining aereal extent of the bioclimatic space, although differing in degree. The results presented in this study should be viewed as a first step towards understanding the trends likely to affect the blanket peatland distribution in Great Britain. The eventual fate of existing blanket peatlands left outside their bioclimatic space remains uncertain.

Divinyldisiloxane and divinylsilane complexes of rhodium(I)

Reaction of the tetrakis(cyclooctene)rhodium(I) complex [{Rh(C8H14-c)2(μ-Cl)}2] with the appropriate divinyldisiloxane molecules (ViSiR2)2O (R=Me or Ph) yields, by displacement of the cycloctene ligands, the complexes [{Rh(ViSiR2)2O(μ-Cl)}2] (R=Me (1) or Ph (2)). These react further with a tertiary phosphine PR3 to give cis-[Rh{(ViSiR2)2O}(PR′3)Cl] (R′=Ph or C6H4Me-p). The complex cis-[{Rh(Vi2SiMe2)(μ-Cl)}2] (7) was similarly prepared by the displacement of ethylene from [{Rh(C2H4)2(μ-Cl)}2] by the divinyldimethylsilane Vi2SiMe2. X-ray molecular structures of the crystalline complexes 1, 2 and 7 show a distorted square planar Rh(I) environment, the CH2CH groups being orthogonal to this plane; 1 and 2 have the Rh–(ViSiR2)2O metallacycle in the chair conformation, but differ in the nature of the central Rh(Cl)RhCl core, which is planar for 1 and puckered for 2, but each of 1 and 2 is the rac-diastereoisomer, whereas 7 has the meso-configuration. In solution 1 and 2 exist as a mixture of isomers, probably the rac- and meso-pairs as established by multinuclear NMR spectral studies. A series of saturation transfer NMR spectroscopic experiments showed that the divinyldisiloxane ligands in [{Rh(ViSiPh2)2O(μ-Cl)}2] underwent a dynamic process involving the dissociation, rotation and then reassociation of the vinyl groups.

A hydrogen-1 nuclear magnetic resonance, mass spectral and extended Hückel study of some olefin complexes of rhodium(I) and iridium(I) and the crystal and molecular structure of η4-2,4-dimethylpenta-1,4-diene(η5-formylcyclopentadienyl)rhodium(I)

A 1H NMR study of monosubstituted η-cyclopentadienyl-rhodium(I) complexes of type LLRh(C5H4X) and -iridium(I) complexes of type L2Ir(C5H4X) (L = ethene, LL = 1,3- or 1,5-diolefin; X = C(C6H5)3, CHO, or COOCH3) has been carried out. For complexes of both metals in which the neutral ligand is ethene or a non-conjugated diolefin the NMR spectra of the cyclopentadienyl protons are unusual in that H(2), H(5) resonate to high field either at room temperature or below. The corresponding NMR spectra for the cyclopentadienyl ring protons of complexes where the neutral ligand is a conjugated diene are, with one exception, normal. A single crystal X-ray structural analysis of (η4-2,4-dimethylpenta-1,4-diene)(η5-formylcyclopentadienyl)rhodium(I) (which exhibits an abnormal 1H NMR spectrum) reveals substantial localisation of electron density in the C(3)C(4) Cp ring bond (1.283(33) Å) which may be consistent with a contribution from an ‘allyl-ene’ rotamer to the ring—metal bonding scheme. An extended Hückel calculation with self consistent charge iteration was performed on this complex. The results predict a greater Mulliken overlap population for the C(3)C(4) bond in the cyclopentadienyl ring and show that the localisation is dependent on both the Cp ring substituent and the nature of the diolefin. The mass spectral fragmentation patterns of some representative diene complexes of iridium(I) and rhodium(I) are presented.

Attribution of climate change: a methodology to estimate the potential contribution to increases in potato yield in Scotland since 1960

Maincrop potato yields in Scotland have increased by 3035 similar to t similar to ha-1 since 1960 as a result of many changes, but has changing climate contributed anything to this? The purpose of this work was to answer this question. Daily weather data for the period 19602006 were analysed for five locations covering the zones of potato growing on the east coast of Scotland (between 55.213 and 57.646 similar to N) to determine trends in temperature, rainfall and solar radiation. A physiologically based potato yield model was validated using data obtained from a long-term field trial in eastern Scotland and then employed to simulate crop development and potential yield at each of the five sites. Over the 47 similar to years, there were significant increases in annual air and 30 similar to cm soil temperatures (0.27 and 0.30 similar to K similar to decade-1, respectively), but no significant changes in annual precipitation or in the timing of the last frost in spring and the first frost of autumn. There was no evidence of any north to south gradient of warming. Simulated emergence and canopy closure became earlier at all five sites over the period with the advance being greater in the north (3.7 and 3.6 similar to days similar to decade-1, respectively) than the south (0.5 and 0.8 similar to days similar to decade-1, respectively). Potential yield increased with time, generally reflecting the increased duration of the green canopy, at average rates of 2.8 similar to t similar to ha-1 decade-1 for chitted seed (sprouted prior to planting) and 2.5 similar to t similar to ha-1 decade-1 for unchitted seed. The measured warming could contribute potential yield increases of up to 13.2 similar to t similar to ha-1 for chitted potato (range 7.119.3 similar to t similar to ha-1) and 11.5 similar to t similar to ha-1 for unchitted potato (range 7.115.5 similar to t similar to ha-1) equivalent to 3439% of the increased potential yield over the period or 2326% of the increase in actual measured yields.

Euthydemoss of Bactria

Euthydemos I (ca. 260–200 bce) was king of Bactria from around 230. He founded a dynasty which, most notably under his son Demetrios I, extended the control of the Greco-Bactrian kings south of the Hindu Kush into Arachosia and India.

Effect of an ancillary ligand on single helix-double helix interconversion in copper complexes. Copper(I)-water bond

Reaction of Cu(ClO(4))(2)center dot 6H(2)O with the 1:2 condensate of benzildihydrazone and 2-acetylpyridine, in methanol in equimolar ratio yields a green compound which upon recrystallisation from 1:1 CH(2)Cl(2)-C(6)H(6) mixture affords [CuL(H(2)O)](ClO(4))(2)center dot 1/2C(6)H(6). The complex crystallises in the space group P-1 with a = 8.028(11) angstrom, b = 12.316(17) angstrom, c = 18.14(3) angstrom, alpha = 97.191(10)degrees, beta = 94.657(10)degrees and gamma = 108.039(10)degrees. It is single helical with the metal having a distorted trigonal bipyramidal N(4)O coordination sphere. The acid dissociation constant of the Cu(I) complex in CH(3)CN is 3.34 +/- 0.19. The X band EPR spectrum of the compound is rhombic with g(1) = 2.43, g(2) = 2.10 g(3) = 2.02 and A(1) = 79.3 x 10(-4) cm(-1). The Cu(II/I) potential of the complex in CH(2)Cl(2) at a glassy carbon electrode is 0.43 V vs SCE. It is argued that the copper-water bond persists in the corresponding copper(I) species. Its implications on the single helix-double helix interconversion in copper helicates are discussed. DFT calculations at the B3LYP/6-311G** level shows that the binding energy of water in the single helicol live-coordinate copper(I) species [CuL(H(2)O)](+) is similar to 40 kJ mol(-1).

Croig Cave: a late Bronze Age ornament deposition and 3,500 years of coastal foraging in NW Mull, Scotland

Activity within caves provides an important element of the later prehistoric and historic settlement pattern of western Scotland. This contribution reports on a small-scale excavation within Croig Cave, on the coast of north-west Mull, that exposed a 1.95m sequence of midden deposits and cave floors that dated bewteen c 1700 BC and AD 1400. Midden analysis indicated the processing of a .... 950 BC, a penannular copper bracelet a discrete ritual episode within the cycle of otherwise potentially mundane activities. Lead isotope analysis indicates an Irish origin for the copper ore. A piece of iron slag within later midden deposits, dated to c 400 BC, along with high frequencies of wood charcoal, suggest that smithing or smelting may have occurred within the cave. High zinc levels in the historic levels of the midden c AD 1200 might indicate intensive processing of seaweed.

Climate-driven expansion of blanket bogs in Britain during the Holocene

Blanket bog occupies approximately 6 % of the area of the UK today. The Holocene expansion of this hyperoceanic biome has previously been explained as a consequence of Neolithic forest clearance. However, the present distribution of blanket bog in Great Britain can be predicted accurately with a simple model (PeatStash) based on summer temperature and moisture index thresholds, and the same model correctly predicts the highly disjunct distribution of blanket bog worldwide. This finding suggests that climate, rather than land-use history, controls blanket-bog distribution in the UK and everywhere else. We set out to test this hypothesis for blanket bogs in the UK using bioclimate envelope modelling compared with a database of peat initiation age estimates. We used both pollen-based reconstructions and climate model simulations of climate changes between the mid-Holocene (6000 yr BP, 6 ka) and modern climate to drive PeatStash and predict areas of blanket bog. We compiled data on the timing of blanket-bog initiation, based on 228 age determinations at sites where peat directly overlies mineral soil. The model predicts large areas of northern Britain would have had blanket bog by 6000 yr BP, and the area suitable for peat growth extended to the south after this time. A similar pattern is shown by the basal peat ages and new blanket bog appeared over a larger area during the late Holocene, the greatest expansion being in Ireland, Wales and southwest England, as the model predicts. The expansion was driven by a summer cooling of about 2 °C, shown by both pollen-based reconstructions and climate models. The data show early Holocene (pre-Neolithic) blanket-bog initiation at over half of the sites in the core areas of Scotland, and northern England. The temporal patterns and concurrence of the bioclimate model predictions and initiation data suggest that climate change provides a parsimonious explanation for the early Holocene distribution and later expansion of blanket bogs in the UK, and it is not necessary to invoke anthropogenic activity as a driver of this major landscape change.

Climate-driven expansion of blanket bogs in Britain during the Holocene

Blanket bog occupies approximately 6% of the area of the UK today. The Holocene expansion of this hyperoceanic biome has previously been explained as a consequence of Neolithic forest clearance. However, the present distribution of blanket bog in Great Britain can be predicted accurately with a simple model (PeatStash) based on summer temperature and moisture index thresholds, and the same model correctly predicts the highly disjunct distribution of blanket bog worldwide. This finding suggests that climate, rather than land-use history, controls blanket-bog distribution in the UK and everywhere else. We set out to test this hypothesis for blanket bogs in the UK using bioclimate envelope modelling compared with a database of peat initiation age estimates. We used both pollen-based reconstructions and climate model simulations of climate changes between the mid-Holocene (6000 yr BP, 6 ka) and modern climate to drive PeatStash and predict areas of blanket bog. We compiled data on the timing of blanketbog initiation, based on 228 age determinations at sites where peat directly overlies mineral soil. The model predicts that large areas of northern Britain would have had blanket bog by 6000 yr BP, and the area suitable for peat growth extended to the south after this time. A similar pattern is shown by the basal peat ages and new blanket bog appeared over a larger area during the late Holocene, the greatest expansion being in Ireland,Wales, and southwest England, as the model predicts. The expansion was driven by a summer cooling of about 2 °C, shown by both pollen-based reconstructions and climate models. The data show early Holocene (pre- Neolithic) blanket-bog initiation at over half of the sites in the core areas of Scotland and northern England. The temporal patterns and concurrence of the bioclimate model predictions and initiation data suggest that climate change provides a parsimonious explanation for the early Holocene distribution and later expansion of blanket bogs in the UK, and it is not necessary to invoke anthropogenic activity as a driver of this major landscape change.