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.

The chemistry of some organotellurium compounds

Tbe formation of Pd(TeR)n and (CuTeR)n from the reaction between telluroesters and Pd(II)or Cu(II) suggested that these organa­tellurium reagents may be useful precursors of RTe- ligands in reactions with transition-metal substrates. Also the formation of telluronium salts Me2RTeI- from the reaction between telluroesters and methyl iodide, together with the above, confirm the cleavage of -cõ-Te bonds rather than -C-Te bonds. The formation of a carboxylic acid from the toluene solution of a ditelluride d palladium(O) complex in the presence of light oxygen (from air) is demonstrated. When the solvent employed is p-xylene an aldehyde is formed.The reaction proceeds via the free radical, RTeO, with Pd(PPh3)4 as a catalyst.It has also been shown that the oxidation of aldehydes to carboxylic acids is catalysed by ditelluride. Spin trapping experiments with PhCH=N(O)But (phenyl-t-butyl-nitrone) have provided evidence that the oxidative addition of an alkyl halide (RX=Mei, BunBr, BusecBr, ButBr, BrCH2-CH=CHCH2Br, and Br(CH2)4Br) to diphenyltelluride and reductive elimination of CH3SCN from Ph2(CH3)Te(NCS) proceeds via radical pathways. A mechanism is proposed for oxidative addition which involves the preformation of a charge transfer complex of alkyl halide and diphenyltelluride.The first step is the formation of a charge transfer complex, and the initial product of the oxidative addition is a "covalent" form of the tellurium(IV)compound. When the radical R is more stable, Ph2TeX2 may be the major tellurium(IV)product. The reaction of RTeNa (R=p-EtOC6H4, Ph) with organic dihalides X2(CH2)n (n=1,2,3,4) affords telluronium salts (n=3,4; X=Cl, Br) the nature of which is discussed.For n=l (X=Br, I)the products are formulated as charge transfer complexes of stoichiometry (RTe)2(CH2).CH2X2• For n=2, elimination of ditelluride occurs with the formation of an alkene. Some 125’Te Mõssbauer data are discussed and it is suggested that the unusually low value of 6 (7.58 mm.s-1 ) for  p-EtO.C6H4.Te)2(cH2)cH2Br2 relates to removal of 5's electronsfrom the spare pair orbltal via the charge transfer interaction. 125Te Mossbauer data for (p-EtO.C6H4)Te(CH2)4Br are typical of a tellurium (IV) compound and in particular ∇ is in the expected range for a telluronium salt. The product of the reaction of Na Te (C6H4.OEt), with 1,3-dibromopropane is, from the Mössbauer data, also a telluronium salt.

Establishment of a reedbed within a created surface water fed wetland nature reserve

In the early 1990's, outline designs for two wetland nature reserves were being prepared: the Teeside International Nature Reserve (TINR) and the Cardiff Bay Barrage Environmental Compensation Measures at Redwick, Gwent. The initial design for both proposals identified reedbed as a desirable habitat for establishment. The initial design works identified the importance of reedbed evapotranspiration [ET(Reed)] within the water budget, however, literature searches identified a paucity of information on this parameter. Field experiments for the measurement of ET(Reed) from Phragmites australis are described for three sites distributed across England and Wales. Reference Crop Evapotranspiration (ETo) was calculated using techniques recommended by the Food and Agriculture Organisation. A technique for the calculation of a reedbed crop coefficient [Kc(Reed)[, from ET(Reed) and ETo data is discussed. Kc(Reed) values produced in the project were found to be similar to those developed previously in continental Europe. Mean monthly and crop development stage Kc(Reed) values are presented which are applicable in the UK and possibly worldwide. A conceptual hydrological model of surface water fed reedbed systems is developed, and used to calculate the hydrological sustainability of reedbed creation areas in the UK. Finally, the water budget model is verified using data from a small clay catchment located on the TINR. In addition, a methodology is developed for the hydrological design of surface water fed reedbed systems, and recommendations required for the feasibility, design and establishment stage of reedbed creation sites. Further research needs are also identified.

The water use rates of reedbed and wet woodland habitats

To create hydrologically sustainable wetlands, knowledge of the water use requirements of target habitats must be known. Extensive literature reviews highlighted a dearth of water-use data associated with large reedbeds and wet woodland habitats and in response to this field experiments were established. Field experiments to measure the water use rates of large reedbeds [ET(Reed)] were completed at three sites within the UK. Reference Crop Evapotranspiration [ETo] was calculated and mean monthly crop coefficients [Kc(Reed)] were developed. Kc(Reed) was less than 1 during the growing season (March to September), ranging between 0.22 in March and reaching a peak of 0.98 in June. The developed coefficients compare favourably with published data from other large reedbed systems and support the premise that the water use of large reedbeds is lower than that from small/fringe reedbeds. A methodology for determining water use rates from wet woodland habitats (UK NVC Code: W6) is presented, in addition to provisional ET(W6) rates for two sites in the UK. Reference Crop Evapotranspiration [ETo] data was used to develop Kc(W6) values which ranged between 0.89 (LV Lysimeter 1) and 1.64 (CH Lysimeter 2) for the period March to September. The data are comparable with relevant published data and show that the water use rates of wet woodland are higher than most other wetland habitats. Initial observations suggest that water use is related to the habitat’s establishment phase and the age and size of the canopy tree species. A theoretical case study presents crop coefficients associated with wetland habitats and provides an example water budget for the creation of a wetland comprising a mosaic of wetland habitats. The case study shows the critical role that the water use of wetland habitats plays within a water budget.