The active sites of the xanthine oxidase and sulfite oxidase enzyme families contain one pterin-dithiolene cofactor ligand bound to a molybdenum atom. Consequently, monodithiolene molybdenum complexes have been sought by exploratory synthesis for structural and reactivity studies. Reaction of [MoO(S(2)C(2)Me(2))(2)](1-) or [MoO(bdt)(2)](1-) with PhSeCl results in removal of one dithiolate ligand and formation of [MoOCl(2)(S(2)C(2)Me(2))](1-) (1) or [MoOCl(2)(bdt)](1-) (2), which undergoes ligand substitution reactions to form other monodithiolene complexes [MoO(2-AdS)(2)(S(2)C(2)Me(2))](1-) (3), [MoO(SR)(2)(bdt)](1-) (R = 2-Ad (4), 2,4,6-Pr(i)(3)C(6)H(2) (5)), and [MoOCl(SC(6)H(2)-2,4,6-Pr(i)(3))(bdt)](1-) (6) (Ad = 2-adamantyl, bdt = benzene-1,2-dithiolate). These complexes have square pyramidal structures with apical oxo ligands, exhibit rhombic EPR spectra, and 3-5 are electrochemically reducible to Mo(IV)O species. Complexes 1-6 constitute the first examples of five-coordinate monodithiolene Mo(V)O complexes; 6 approaches the proposed structure of the high-pH form of sulfite oxidase. Treatment of [MoO(2)(OSiPh(3))(2)] with Li(2)(bdt) in THF affords [MoO(2)(OSiPh(3))(bdt)](1-) (8). Reaction of 8 with 2,4,6-Pr(i)(3)C(6)H(2)SH in acetonitrile gives [MoO(2)(SC(6)H(2)-2,4,6-Pr(i)(3))(bdt)](1-) (9, 55%). Complexes 8 and 9 are square pyramidal with apical and basal oxo ligands. With one dithiolene and one thiolate ligand of a square pyramidal Mo(VI)O(2)S(3) coordination unit, 9 closely resembles the oxidized sites in sulfite oxidase and assimilatory nitrate reductase as deduced from crystallography (sulfite oxidase) and Mo EXAFS. The complex is the first structural analogue of the active sites in fully oxidized members of the sulfite oxidase family. This work provides a starting point for the development of both structural and reactivity analogues of members of this family.

The climatological features of the winter snow depth over the Tibetan Plateau and the summer precipitation in China are diagnosed using datasets obtained from 78 snow observation stations and 160 rainfall stations during 1957 to 1998. The climatic effects of the snow anomaly over the Tibetan Plateau on the regional summer monsoon climate in China are diagnosed and numerically simulated by use of a regional climate model (RegCM2). The singular value decomposition technique is adopted to diagnose the relationships between the previous winter and spring plateau snow depth anomalies and the spring and summer regional precipitation in China. It is found that the snow depth anomaly, especially in winter, is one of the factors influencing precipitation in China; however, it is perhaps not the only one, and even not the most important one. Nevertheless, it is proved that the winter snow anomaly over the Tibetan Plateau is relatively more important than that in spring for the regional precipitation in China. Results of numerical simulations show that the snow anomaly over the plateau has effects that are evident on China's summer monsoon climate. The increase of both snow cover and snow depth can delay the onset and weaken the intensity of the summer monsoon obviously, resulting in a decrease in precipitation in southern China and an increase in the Yangtze and Huaihe River basins. The influence of the winter snow depth is more substantial than that of both the winter snow cover and the spring snow depth. The mechanism of how the plateau snow anomaly influences the regional monsoon climate is briefly analysed. It is found that snow anomalies over the Tibetan Plateau change the soil moisture and the surface temperature through the snowmelt process at first, and subsequently alter heat, moisture and radiation fluxes from the surface to the atmosphere. Abnormal circulation conditions induced by changes of surface fluxes may affect the underlying surface properties in turn. Such a long-term interaction between the wetland and the atmosphere is the key process resulting in later climatic changes.

No abstract

Synthetic models leading to oxosulfidotungsten(VI) groups and dithiolene chelate rings have been investigated. The heterogeneous reaction systems [WO4-nSn]2-/2Ph3SiCl/Me4phen (n = 0-2) in acetonitrile afford the complexes [WQ2(OSiPh3)2(Me4phen)] (1-3) in the indicated yields containing the groups W(VI)O2 (1; 86%), W(VI)O2 (2; 45%), and W(VI)S2 (3; 83%). In the crystalline state these complexes have imposed C2 symmetry, with cis-oxo/sulfido and trans-silyloxide ligands. 1H NMR spectra indicate that this stereochemistry is retained in solution. The colors of 2 (yellow, 367 nm) and 3 (orange, 451 nm) arise from LMCT absorptions at the indicated wavelengths. These results demonstrate that the silylation procedure previously introduced for the preparation of molecules with the Mo(VI)OS group (Thapper, et al. Inorg. Chem. 1999, 38, 4104) extends to tungsten. Methods for the formation of dithiolene chelate rings MS2C2R2 in reactions with sulfide-bound M = Mo or W precursors are summarized. In a known reaction type, 3 and activated acetylenes rapidly form [W(IV)(OSiPh3)2(Me4phen)(S2C2R2)] (R = CO2Me, 4, 83%, and Ph, 5, 98%). In a new reaction type not requiring the isolation of an intermediate, the systems [MO2S2]2-/2Ph3SiCl/Me4phen/PhC=CPh in acetonitrile afford 5 (68%) and [Mo(IV)(OSiPh3)2(Me4phen)(S2C2Ph2)] (6; 61%). Complexes 5 and 6 are isostructural, maintain the trans-silyloxide stereochemistry, and exhibit chelate ring dimensions indicative of ene- 1,2-dithiolate coordination. Reductions in the -1.4 to -1.7 V range are described as metal-centered. It remains to be seen whether the oxo/sulfidotungsten(VI) groups in 1-3 eventuate in the active sites of tungstoenzymes. (Me4phen = 3,4,7,8-tetramethyl-1,10-phenanthroline.)

SUMMARYIn the context of a regional climate model (RegCM2), simulation is undertaken of climatic effects of changed vegetation over China with their possible mechanisms studied, reaching results which show that the increase in ood events over the Yangtze-Huai River valleys and the aggravation of north-China droughts are likely to be under the joint action of deserti cation of the northern grassland, and southern degradation of evergreen broadleaf trees, the latter seeming to be the primary factor. Severe vegetation degeneration leads to a positive feedback between rainfall reduction and degradation with the consequence that the disaster expands steadily outward and the area affected is dif cult to turn back into farmland. In contrast, less heavy degeneration causes a negative feedback between deterioration and rainfall reduction, and the stricken sector is likely to be reclaimed when human damages are decreased or removed. However, degeneration strengthens surface runoff, allowing ood occurrence. Vegetation deterioration makes the climate even more inhospitable. On the other hand, experiments show that the vegetation enlargement of northern grassland will lead to a mild climate, responsible for precipitation reduction in the outer belts of afforestation, possibly causing newly-planted trees to die stepwise inwardly, a result that means the current climate in the grassy land does not seem to support a plan of large-scale afforestation there. Study of climatic response to changed surface roughness and albedo shows that the former more strongly affects rainfall, atmospheric circulation patterns and humidity eld, and the latter strongly affects temperature. Moreover, surface-released effective thermal uxes (sensible and latent heat) follow the change in vegetation, and so does their Bowen ratio, thereby resulting in a change in moist static energy distribution in the atmosphere, followed by a corresponding alteration of atmospheric strati cation and vertical motion, which, in turn, affects vapour transportation that, in connection with changed vertical motion, leads to rainfall variation.