The co-ordination chemistry of tellurium and related selenium ligands

2-(2-pyridyl)phenyl(p-ethoxyphenyl)tellurium(II), (RR1Te) reacts with HgC12 at room temperature to give white HgCl2.RR1Te. On setting aside, or on warming the reaction mixture a yellow material, [R1HgCl.(RTeCl)2] is formed. Multinuclear NMR(125Te, 199Hg, 1H) and mass spectroscopy confirm the formulation, and confirm the ease of transfer of the p-ethoxyphenyl group (R1) between the metal centres. The crystal structure of the yellow material consists of two discrete RTeCl molecules together with a R1HgCl molecule. There is no dative bond formation between these species, hence the preferred description of the formation of an inclusion complex. The reaction of RR1Te with Copper(I) chloride in the cold gives an air sensitive yellow product Cu3Cl3(RR1Te)2(0.5CH3CN); under reflux in air changes to the green Cu2Cl(RR1Te)(0.5 EtOH). By contrast, the reaction of RR1Te with acetonitrile solution of Copper(II) salts under mild conditions affords the white materials CuCl(RR1Te) and CuBr(RR1Te)H2O. RR1Te reacts with PdCl2 and PtCl2 to give materials albeit not well defined, can be seen as intermediates to the synthesis of inorganic phase of the type M3XTe2XCl2X. Paramagnetism is associated with some of the palladium and platinum products. The 195Pt NMR measurement in DMSO establishes the presence of six platinum species, which are assigned to Pt(IV), Pt(III) or Pt(II). The reactions show that in the presence of PdCl2 or PtCl2 both R and R1 are very labile. The reaction of RHgCl(R= 2-(2-pyridyl)phenyl) with SeX4(X= Cl, Br) gives compounds which suggest that both Trans-metallation and redox processes are involved. By varying reaction conditions materials which appear to be intermediates in the trans-metallation process are isolated. Potentially bidentate tellurium ligands having molecular formula RTe(CH2)nTeR,Ln, (R= Ph,(t-Bu). C6H4, n = 5,10) are prepared. Palladium and Platinum complexes containing these ligands are prepared. Also complex Ph3SnC1L(L = p-EtO.C6H4) is prepared.

Diagenesis and aquifer characteristics of the Sherwood Sandstone Group in North Nottinghamshire

The Sherwood Sandstone Group forms an important aquifer in Eastern England, which in North Nottinghamshire comprises the Nottingham Castle and Lenton Sandstone Formations. The aquifer is formed by an alluvial red-bed sequence dominated by medium-coarse grained sandstones which are texturally immature to submature and have only been subjected to shallow burial diagenesis. These sandstones reached the mature stage of the meso diagenetic regime, and four stages are recognized in their diagenetic history depending upon the physical/chemical processes prevailing and the subsequent effect on porosity and permeability. Stage "One" represents changes including dissolution of unstable silicates, clay replacement, red colouration and precipitation of authigenic minerals (quartz, feldspar, illite, l/S, kaolinite, dolomite, ferroan calcite, calcite). The net result of these changes was porosity reduction. Stage "Two" included changes due to mechanical compaction which resulted in minor porosity reduction. Stage "Three" was the main phase of secondary porosity enhancement. Stage "Four" represents changes taking place in the present groundwater where porosity and permeability may have been increased by dissolution and partly reduced by kaolinite precipitation. Porosity measured by water-resaturation and Hg-injection gave average values of 25.63% and 24.85% respectively. The results are comparable and showed marked correlation especially in highly porous/permeable rocks. Porosity measurements from photomicrographs were markedly offset from laboratory results. Horizontal Kw ranged between 1.43 x 10-5 and 1.13 x 10-1 mm/sec, with an average of  1.68 x 10-2 mm/sec. The estimated KHg ranged between 7.29 x 10-6 and 6.99 x 10-2 mm/sec with an average of 1.47 x 10-2 mm/sec. Both results are significantly correlated for highly porous/permeable rocks. The hydraulic properties are highly dependent upon the diagenetic properties (as most of the pores present are of secondary origin) as well as the pore size distribution. The chemistry of these groundwaters indicates that they are under-saturated with respect to dolomite, calcite, K-feldspar, l/S clay, and montmorillonite. The precipitation of kaolinite,and to a lesser extent illite, is favoured in the present groundwater regime.