Synthesis, structure and solution chemistry of quaternary oxovanadium(V) complexes incorporating hydrazone ligands

[VIVO(acac)(2)] reacts with an equimolar amount of benzoyl hydrazone of 2-hydroxyacetophenone (H2L1) or 5-chloro-2-hydroxyacetophenone (H2L2) in the presence of excess pyridine (py) in methanol to produce the quaternary [(VO)-O-V(L-1)(OCH3)(py)] (1) and [(VO)-O-V(L-2)(OCH3)(py)] (2) complexes, respectively, while under similar condition, the benzoyl hydrazones of 2-hydroxy-5-methylacetophenone (H2L3) and 2-hydroxy-5-methoxyacetophenone (H2L4) afforded only the methoxy bridged dimeric [(VO)-O-V(L-3/L-4)(OCH3)](2) complexes. The X-ray structural analysis of 1 and 2 indicates that the geometry around the metal is distorted octahedral where the three equatorial positions are occupied by the phenolate-O, enolate-O and the imine-N of the fully deprotonated hydrazone ligand in its enolic form and the fourth one by a methoxide-O atom. An oxo-O and a pyridine-N atom occupy two axial positions. Quaternary complexes exhibit one quasi-reversible one-electron reduction peak near 0.25 V versus SCE in CH2Cl2 and they decompose appreciably to the corresponding methoxy bridged dimeric complex in CDCl3 solution as indicated by their H-1 NMR spectra. These quaternary VO3+ complexes are converted to the corresponding V2O34+-complexes simply on refluxing them in acetone and to the VO2+-complexes on reaction with KOH in methanol. An equimolar amount of 8-hydroxyquinoline (Hhq) converts these quaternary complexes to the ternary [(VO)-O-V(L)(hq)] complexes in CHCl3. (C) 2009 Elsevier B. V. All rights reserved.

An extension of the well-known quaternary section at Godrevy, St Ives Bay, West Cornwall: analysis and review

The well-known Quaternary section at Godrevy, west Cornwall has been often described during the past half century, however, a further section, about a kilometre to the south is considered for the first time since a brief mention at the beginning of the last century. This 200m long exposure rests upon a raised shore platform and consists of a basal raised beach and littoral sand, overlain by a local diamict revealing evidence of post-depositional frost disturbance and finally Holocene dune sand. It is proposed that this Strap Rock site be included within the general discussion of the Godrevy section.

The sea-level conundrum: case studies from palaeo-archives

Uncertainties in sea-level projections for the 21st century have focused ice sheet modelling efforts to include the processes that are thought to be contributing to the recently observed rapid changes at ice sheet margins. This effort is still in its infancy, however, leaving us unable to make reliable predictions of ice sheet responses to a warming climate if such glacier accelerations were to increase in size and frequency. The geological record, however, has long identified examples of nonlinear ice sheet response to climate forcing (Shackleton NJ, Opdyke ND. 1973. Oxygen isotope and paleomagnetic stratigraphy of equatorial Pacific core V28–239, late Pliocene to latest Pleistocene. Geological Society of America Memoirs145: 449–464; Fairbanks RG. 1989. A 17,000 year glacio-eustatic sea level record: influence of glacial melting rates on the Younger Dryas event and deep ocean circulation. Nature342: 637–642; Bard E, Hamelin B, Arnold M, Montaggioni L, Cabioch G, Faure G, Rougerie F. 1996. Sea level record from Tahiti corals and the timing of deglacial meltwater discharge. Nature382: 241–244), thus suggesting an alternative strategy for constraining the rate and magnitude of sea-level change that we might expect by the end of this century. Copyright © 2009 John Wiley & Sons, Ltd.

Organocatalytic domino reaction of cyanosulfones: access to complex cyclohexane systems with quaternary carbon centers

When ε-nitro-a,β-unsaturated esters are added to conjugated cyanosulfones in the presence of a bifunctional thiourea catalyst, a highly stereoselective domino reaction occurs to generate complex cyclohexanes with up to four stereogenic centers, one of which is quaternary in nature. Therefore, it is demonstrated that, like nitro compounds, sulfones can undergo an asymmetric intramolecular conjugate addition to r,β- unsaturated esters in the presence of a bifunctional organocatalyst.

Species-specific responses of Late Quaternary megafauna to climate and humans

Despite decades of research, the roles of climate and humans in driving the dramatic extinctions of large-bodied mammals during the Late Quaternary period remain contentious. Here we use ancient DNA, species distribution models and the human fossil record to elucidate how climate and humans shaped the demographic history of woolly rhinoceros, woolly mammoth, wild horse, reindeer, bison and musk ox. We show that climate has been a major driver of population change over the past 50,000 years. However, each species responds differently to the effects of climatic shifts, habitat redistribution and human encroachment. Although climate change alone can explain the extinction of some species, such as Eurasian musk ox and woolly rhinoceros, a combination of climatic and anthropogenic effects appears to be responsible for the extinction of others, including Eurasian steppe bison and wild horse. We find no genetic signature or any distinctive range dynamics distinguishing extinct from surviving species, emphasizing the challenges associated with predicting future responses of extant mammals to climate and human-mediated habitat change.

Late Quaternary fire regimes of Australasia

We have compiled 223 sedimentary charcoal records from Australasia in order to examine the temporal and spatial variability of fire regimes during the Late Quaternary. While some of these records cover more than a full glacial cycle, here we focus on the last 70,000 years when the number of individual records in the compilation allows more robust conclusions. On orbital time scales, fire in Australasia predominantly reflects climate, with colder periods characterized by less and warmer intervals by more biomass burning. The composite record for the region also shows considerable millennial-scale variability during the last glacial interval (73.5–14.7 ka). Within the limits of the dating uncertainties of individual records, the variability shown by the composite charcoal record is more similar to the form, number and timing of Dansgaard–Oeschger cycles as observed in Greenland ice cores than to the variability expressed in the Antarctic ice-core record. The composite charcoal record suggests increased biomass burning in the Australasian region during Greenland Interstadials and reduced burning during Greenland Stadials. Millennial-scale variability is characteristic of the composite record of the sub-tropical high pressure belt during the past 21 ka, but the tropics show a somewhat simpler pattern of variability with major peaks in biomass burning around 15 ka and 8 ka. There is no distinct change in fire regime corresponding to the arrival of humans in Australia at 50 ± 10 ka and no correlation between archaeological evidence of increased human activity during the past 40 ka and the history of biomass burning. However, changes in biomass burning in the last 200 years may have been exacerbated or influenced by humans.

Late Quaternary highstands at Lake Chilwa, Malawi: frequency, timing and possible forcing mechanisms in the last 44ka

The extensive shoreline deposits of Lake Chilwa, southern Malawi, a shallow water body today covering 600 km2 of a basin of 7500 km2, are investigated for their record of late Quaternary highstands. OSL dating, applied to 36 samples from five sediment cores from the northern and western marginal sand ridges, reveal a highstand record spanning 44 ka. Using two different grouping methods, highstand phases are identified at 43.7–33.3 ka, 26.2–21.0 ka and 17.9–12.0 ka (total error method) or 38.4–35.5 ka, 24.3–22.3 ka, 16.2–15.1 ka and 13.5–12.7 ka (Finite Mixture Model age components) with two further discrete events recorded at 11.01 ± 0.76 ka and 8.52 ± 0.56 ka. Highstands are comparable to the timing of wet phases from other basins in East and southern Africa, demonstrating wet conditions in the region before the LGM, which was dry, and a wet Lateglacial, which commenced earlier in the southern compared to northern hemisphere in East Africa. We find no evidence that wet phases are insolation driven, but analysis of the dataset and GCM modelling experiments suggest that Heinrich events may be associated with enhanced monsoon activity in East Africa in both timing and as a possible causal mechanism.

Late Quaternary hydrological dynamics in the Middle Kalahari: forcing and feedbacks

The Kalahari region has become a major source of Quaternary palaeoenvironmental data derived primarily from the analysis of geomorphological proxies of environmental change. One suite of data, from palaeolacustrine landforms, has recently provided a new record of major hydrological changes in the last 150 ka [Burrough, S. L., Thomas, D. S. G., Bailey, R. M., 2009. Mega-Lake in the Kalahari: A Late Pleistocene record of the Palaeolake Makgadikgadi system. Quaternary Science Reviews, in press.]. Here we present an improved analysis of the drivers and feedbacks of lake level change, utilising information from three main sources: data from the lake system itself, from analyses of other late Quaternary records within the region and from climate modelling. Simulations using the Hadley Centre coupled climate model, HadCM3, suggest that once triggered, the lake body was large enough to potentially affect both local and regional climates. Surface waters and their interactions with the climate are therefore an important component of environmental dynamics during the late Quaternary. Through its capacity to couple Middle Kalahari environments to distant forcing mechanisms and to itself force environmental change, we demonstrate that the existence or absence of megalake Makgadikgadi adds a new level of complexity to the interpretations of environmental proxy records in southern Africa's summer rainfall zone.

Palaeovegetation in China during the late Quaternary: Biome reconstructions based on a global scheme of plant functional types

Two previous reconstructions of palaeovegetation across the whole of China were performed using a simple classification of plant functional types (PFTs). Now a more explicit, global PFT classification scheme has been developed, and a substantial number of additional pollen records have become available. Here we apply the global scheme of PFTs to a comprehensive set of pollen records available from China to test the applicability of the global scheme of PFTs in China, and to obtain a well-founded reconstruction of changing palaeovegetation patterns. A total of 806 pollen surface samples, 188 mid-Holocene (MH, 6000 14C yr BP) and 50 last glacial maximum (LGM, 18,000 14C yr BP) pollen records were used to reconstruct vegetation patterns in China, based on a new global classification system of PFTs and a standard numerical technique for biome assignment (biomization). The biome reconstruction based on pollen surface samples showed convincing agreement with present potential natural vegetation. Coherent patterns of change in biome distribution between MH, LGM and present are observed. In the MH, cold and cool-temperate evergreen needleleaf forests and mixed forests, temperate deciduous broadleaf forest, and warm-temperate evergreen broadleaf and mixed forest in eastern China were shifted northward by 200–500 km. Cold-deciduous forest in northeastern China was replaced by cold evergreen needleleaf forest while in central northern China, cold-deciduous forest was present at some sites now occupied by temperate grassland and desert. The forest–grassland boundary was 200–300 km west of its present position. Temperate xerophytic shrubland, temperate grassland and desert covered a large area on the Tibetan Plateau, but the area of tundra was reduced. Treeline was 300–500 m higher than present in Tibet. These changes imply generally warmer winters, longer growing seasons and more precipitation during the MH. Westward shifts of the forest–shrubland–grassland and grassland–desert boundaries imply greater moisture availability in the MH, consistent with a stronger summer monsoon. During the LGM, in contrast, cold-deciduous forest, cool-temperate evergreen needleleaf forest, cool mixed forests, warm-temperate evergreen broadleaf and mixed forest in eastern China were displaced to the south by 300–1000 km, while temperate deciduous broadleaf forest, pure warm-temperate evergreen forest, tropical semi-evergreen and evergreen broadleaf forests were restricted or absent from the mainland of southern China, implying colder winters than present. Strong shifts of temperate xerophytic shrubland, temperate grassland and desert to the south and east in northern and western China and on the Tibetan Plateau imply drier conditions than present.