Synthesis of novel ferrocenylphosphine-amidine ligands with central and planar chirality and their diastereomeric effect in Pd-catalyzed asymmetric allylic alkylation

Some novel ferrocenylphosphine-amidine ligands with central and planar chirality were prepared from (R,S-p)-PPFNH2-R 3 and its diastereomer (S,S-p)-PPFNH2 3a. The efficiency and diastereomeric impact of these ferrocenylphosphine-amidine ligands in the palladium-catalyzed asymmetric allylic substitution was examined, and up to 96% e.e. with 98% yield was achieved by the use of ligand (R,S-p)-4a with a methyl group in the amidino moiety. The results also indicated that (R)-central chirality and (S-p)-planar chirality in these ferrocenylphosphine-amidine ligands were matched for the palladium-catalyzed asymmetric allylic alkylation. (C) 2003 Elsevier Ltd. All rights reserved.

Synthesis of novel P-ketimine bidentate ferrocenyl ligands with central and planar chirality and comparsion in the catalytic activity between P-ketimine and P-aldimine

A series of novel ferrocenylphosphine-ketimine ligands 6 were prepared by reaction of (R,S-p)-PPFNH2-R or (S,S-p)-PPFNH2 with a variety of m-substituted acetophenones. A different catalytic activity was observed between ferrocenylphosphine-ketimine ligands and corresponding aldimine ligands. The efficiency and diastereomeric impact of these ferrocenylphosphine-ketimine ligands in Pd-catalyzed asymmetric allylic alkylation were first investigated, and higher enantioselectivity of over 98% e.e. with 95% yield was obtained by the use of ferrocenylphosphine-ketimine ligands. However, in Rh-catalyzed asymmetric hydrosilylation of aryl ketones, only 42% e.e. was obtained by the use of ferrocenylphosphine-ketimine ligands compared to 90% e.e. with the use of aldimine ligands. (C) 2003 Elsevier Ltd. All rights reserved.

Reconstructing temperature change in Central East China during 601-920 AD

Chinese Academy of Sciences [KZCX2-YW-Q1-01, KZCX2-YW-315]; National Natural Science Foundation of China [40625002]

Radiolarian distribution in surface sediments of the northern and central South China Sea

Radiolarian distribution in surface sediments of 104 stations from northern and central South China Sea show that the abundance and diversity of radiolarians increase with the water depth and are related to radiolarian concentrations from the water column, diminished terrigenous input, variability in calcareous shell content and the rate of silica and carbonate dissolution in the deep sea. According to the appearances of individual species in surface sediments at particular depths, seven faunal boundaries distribution are recognized at water depths of 100, 450, 650, 1000, 1200, 1400 and 2500 m. Four radiolarian assemblages in the sediments were identified by applying clustering procedures. Geographic distributions of these four assemblages coincide with present-day hydrologic features of the surface waters in this area.

A comprehensive investigation of an offshore active fault in the Western Sagami Bay, central Japan

Offshore active faults, especially those in the deep sea, are very difficult to study because of the water and sedimentary cover. To characterize the nature and geometry of offshore active faults, a combination of methods must be employed. Generally, seismic profiling is used to map these faults, but often only fault-related folds rather than fracture planes are imaged. Multi-beam swath bathymetry provides information on the structure and growth history of a fault because movements of an active fault are reflected in the bottom morphology. Submersible and deep-tow surveys allow direct observations of deformations on the seafloor (including fracture zones and microstructures). In the deep sea, linearly aligned cold seep communities provide indirect evidence for active faults and the spatial migration of their activities. The Western Sagami Bay fault (WSBF) in the western Sagami Bay off central Japan is an active fault that has been studied in detail using the above methods. The bottom morphology, fractured breccias directly observed and photographed, seismic profiles, as well as distribution and migration of cold seep communities provide evidence for the nature and geometry of the fault. Focal mechanism solutions of selected earthquakes in the western Sagami Bay during the period from 1900 to 1995 show that the maximum compression trends NW-SE and the minimum stress axis strikes NE-SW, a stress pattern indicating a left-lateral strike-slip fault.

Resuspension and advection processes affecting suspended particulate matter concentrations in the central English Channel

Suspended particulate matter (SPM) measurements obtained along a cross-section in the central English Channel (Wight-Cotentin transect) indicate that the area may be differentiated into: (1) an English coastal zone, associated with the highest concentrations; (2) a French coastal zone, with intermediate concentrations; and (3) the offshore waters of the Channel, characterised by a very low suspended-sediment load. The SPM particle-size distribution was modal close to the English coast (main mode 10-12 mu m); the remainder of the area was characterised by flat SPM distributions. Examination of the diatom communities in the SPM suggest:; that material resuspended in the intertidal zone and the estuarine environments was advected towards the offshore waters of the English Channel. Considerable variations in SPM concentrations occurred during a tidal cycle: maximum concentrations were sometimes up to 3 times higher than the minimum concentrations, Empirical orthogonal function (EOF) analysis of the SPM concentration time series indicates that, although the bottom waters were more turbid than the surficial waters, this was not likely to be the result of in situ sediment resuspension. Instead, the observed variations appear to be controlled mainly by advective mechanisms. The limited resuspension was probably caused by: (1) the limited availability of fine-grained material within the bottom sediments, and (2) 'bed-armouring' processes which protect the finer-grained fractions of the seabed material from erosion and entrainment within the overlying flow during the less energetic stages of the tide.

He, Ne and Ar isotopic composition of Fe-Mn crusts from the western and central Pacific Ocean and implications for their genesis

The noble gas nuclide abundances and isotopic ratios of the upmost layer of Fe-Mn crusts from the western and central Pacific Ocean have been determined. The results indicate that the He and Ar nuclide abundances and isotopic ratios can be classified into two types: low He-3/He-4 type and high He-3/He-4 type. The low He-3/He-4 type is characterized by high He-4 abundances of 191x10(-9) cm(3.)STP(.)g(-1) on average, with variable He-4, Ne-20 and Ar-40 abundances in the range (42.8-421)x10(-9) cm(3.)STP(.)g(-1), (5.40-141)x10(-9)cm(3.)STP(.)g(-1), and (773-10976)x10(-9) cm(3.)STP(.)g(-1), respectively. The high He-3/He-4 samples are characterized by low He-4 abundances of 11.7x10(-9) cm(3.)STP(.)g(-1) on average, with He-4, Ne-20 and Ar-40 abundances in the range of (7.57-17.4)x10(-9) cm(3.)STP(.)g(-1), (110.4-25.5)x10(-9) cm(3.)STP(.)g(-1) and (5354-9050)x10(-9) cm(3.)STP(.)g(-1), respectively. The low He-3/He-4 samples have He-3/He-4 ratios (with RIRA ratios of 2.04-2.92) which are lower than those of MORB (R/R-A=8 +/- 1) and Ar-40/Ar-36 ratios (447-543) which are higher than those of air (295.5). The high He-3/He-4 samples have He-3/He-4 ratios (with R/R-A ratios of 10.4-12.0) slightly higher than those of MORB (R/R-A=8 +/- 1) and Ar-40/Ar-36 ratios (293-299) very similar to those of air (295.5). The Ne isotopic ratios (Ne-20/Ne-22 and Ne-21/Ne-22 ratios of 10.3-10.9 and 0.02774-0.03039, respectively) and the Ar-38/Ar-36 ratios (0.1886-0.1963) have narrow ranges which are very similar to those of air (the Ne-20/Ne-22, Ne-21/Ne-22, Ar-38/Ar-36 ratios of 9.80, 0.029 and 0.187, respectively), and cannot be differentiated into different groups. The noble gas nuclide abundances and isotopic ratios, together with their regional variability, suggest that the noble gases in the Fe-Mn crusts originate primarily from the lower mantle. The low He-3/He-4 type and high He-3/He-4 type samples have noble gas characteristics similar to those of HIMU (High U/Pb Mantle)- and EM (Enriched Mantle)-type mantle material, respectively. The low He-3/He-4 type samples with HIMU-type noble gas isotopic ratios occur in the Magellan Seamounts, Marcus-Wake Seamounts, Marshall Island Chain and the Mid-Pacific Seamounts whereas the high He-3/He-4 type samples with EM-type noble gas isotopic ratios occur in the Line Island Chain. This difference in noble gas characteristics of these crust types implies that the Magellan Seamounts, Marcus-Wake Seamounts, Marshall Island Chain, and the Mid-Pacific Seamounts originated from HIMU-type lower mantle material whereas the Line Island Chain originated from EM-type lower mantle material. This finding is consistent with variations in the Pb-isotope and trace element signatures in the seamount lavas. Differences in the mantle surce may therefore be responsible for variations in the noble gas abundances and isotopic ratios in the Fe-Mn crusts. Mantle degassing appears to be the principal factor controlling noble gas isotopic abundances in Fe-Mn crusts. Decay of radioactive isotopes has a negligible influence on the nuclide abundances and isotopic ratios of noble gases in these crusts on the timescale of their formation.

Os isotope dating and growth hiatuses of Co-rich crust from central Pacific

Up to now, accurate determination of the growth age and hiatuses of the Co-rich crust is still a difficult work, which constrains the researches on the genesis, growth process, controlling factors, regional tectonics, paleo-oceanographic background, etc. of the Co-rich crust. This paper describes our work in determining the initial growth age of the Co-rich crust to be of the late Cretaceous Campanian Stage (about 75-80 Ma), by selecting the Co-rich crust with clear multi-layer structures in a central Pacific seamount for layer-by-layer sample analysis and using a number of chronological methods, such as Co flux dating, dating by correlation with Os-187/Os-188 evolution curves of seawater, and stratigraphic division by calcareous nannofossils. We have also discovered growth hiatuses with different time intervals in the early Paleocene, middle Eocene, late Eocene and early-middle Miocene, respectively. These results have provided an important age background for further researches on the Co-rich crust growth process and the paleo-oceanographic environment evolution thereby revealed in the said region.

Distribution pattern of marine flagellate and its controlling factors in the central and north part of the Huanghai Sea in early summer

A survey was carried out in the central and north part of the Huanghai Sea (34.5degrees similar to 37.0degreesN, 120.5degrees similar to124.0degreesE) during June 12 similar to 27, 2000. It was found that the abundance of marine flagellate ranged from 45 to 1278 cell/ml, 479 cell/ml in average. Flagellate was more abundant in the central part than in the north part of Huanghai Sea, and the abundance decreased with the increasing distance from the coast, showing a similar distribution pattern with isotherm. Vertically, high density of flagellate was always presented in the bottom of thermocline, and formed a dense accumulation in the central area of the Huanghai Sea Cold Water Mass. The effects of physical and biological factors on the distribution of marine flagellate in early summer were discussed. Water temperature (especially the existence of thermocline) rather than salinity showed significant effect on the distribution pattern of marine flagellate in the Huanghai Sea in early summer. When comparing the abundance of marine flagellate with that of other microorganisms, it revealed a comparatively stable relationship among these organhisms, with a ratio of heterotrophic bacteria: cyanobacteria: flagellate: dinoflagellate: ciliate being 10(5) 10(3):10(2):10(1):10(0).