Tin and mercury

This chapter contains sections titled: Introduction Geogenic Occurrence Sources of Soil Contamination Chemical Behaviour in Soils Risks from Tin and Mercury in Soils References

A novel copper(I) complex that is a monomeric single helix in solid state but a dimeric double helix in solution

Single helical [(CuL)-L-I]ClO4.12CH(2)Cl(2) (L=1:2 condensate of benzil dihydrazone and 2-acetylpyridine) unfolds and coils up in CH2Cl2 solution to generate double helical [(Cu2L2)-L-I](2+).

Tin and tin-titanium as catalyst components for reversible hydrogen storage of sodium aluminium hydride

This paper is concerned with the effects of adding tin and/or titanium dopant to sodium aluminium hydride for both dehydrogenation and re-hydrogenation reactions during their reversible storage of molecular hydrogen. Temperature programmed decomposition (TPD) measurements show that the dehydrogenation kinetics of NaAlH4 are significantly enhanced upon doping the material with 2 mol% of tributyltin hydride, Sn(Bu)(3)H but the tin catalyst dopant is shown to be inferior than titanium. On the other hand, in this preliminary work, a significant synergetic catalytic effect is clearly revealed in material co-doped with both titanium and tin catalysts which shows the highest reversible rates of dehydrogenation and re-hydrogenation (after their hydrogen depletion). The re-hydrogenation rates of depleted Sn/Ti/NaAlH4 evaluated at both 9.5 and 140 bars hydrogen are also found to be favourable compared to the Ti/NaAlH4, which clearly suggest the importance of the catalyst choice. Basing on these results some mechanistic insights for the catalytic reversible dehydrogenation and re-hydrogenation processes of Sn/Ti/NaAlH4 are therefore made. (C) 2006 Elsevier Ltd. All rights reserved.

Thermoselective phase property of silica tethered with fluorinated chains for controlled 'release' and 'capture' of catalytic fluorous tin species

The temperature dependent mixing of organic and fluorous phases is one of the key principals of fluorous biphasic systems (FBS). Given the high cost of the perfluorous solvents and their impacts to the environment, it is apparent that elimination of these solvents in bulk quantity in the FBS is advantageous. We report for the first time, the surface coverage of silica with a fluorous solvent like material that traps (at ambient temperatures) and releases (at elevated temperatures) a fluorous tin bromide in organic solvent. Here, we demonstrate the catalytic utilisation of this species for the hydrocyclisation of 6-bromo-1-hexene with NaBH4. (C) 2002 Elsevier Science B.V. All rights reserved.

Chemistry of mixed-ligand methoxy bonded oxidovanadium(V) complexes with a family of hydrazone ligands containing VO3+ core and their substituent controlled methoxy-bridged dimeric forms

[(VO)-O-IV(acac)(2)] reacts with an equimolar amount of benzoyl hydrazones of 2-hydroxyacetophenone (H2L1), 2-hydroxy-5-methylacetophenone (H2L2) and 5-chloro-2-hydroxyacetophenone (H2L4) in methanol to afford the penta-coordinated mixed-ligand methoxy bonded oxidovanadium(V) complexes [(VO)-O-V(L-1)-(OCHA(3))](1). [(VO)-O-V(L-2)(OCH3)](2), and [(VO)-O-V(L-4)(OCH3)](4), respectively, whereas, the similar reaction with the benzoyl hydrazone of 2-hydroxy-5-methoxyacetophenone (H2L3) producing only the hexa-coordinated dimethoxy-bridged dimeric complex [(VO)-O-V(L-3)(OCH3)](2) (3A). Similar type of hexa-coordinated dimeric analogue of 1 i.e., [(VO)-O-V(L-1)(OCH3)](2) (1A) was obtained from the reaction of [(VO)-O-IV(acac)(2)] with the equimolar amount of H2L1 in presence of half equivalent 4,4'-bipyridine in methanol while the decomposition of [(VO)-O-IV(L-2)(bipy)] complex in methanol afforded the dimeric analogue of 2 i.e., [(VO)-O-V(L-2)(OCH3)](2) (2A). All these dimeric complexes 1A-3A react with an excess amount of imidazole in methanol producing the respective monomeric complex. The X-ray structural analysis of 1-3 and their dimeric analogues 1A-3A indicates that the geometry around the vanadium center in the monomeric form is distorted square-pyramidal while that of their respective dimeric forms is distorted octahedral, where the ligands are bonded to vanadium meridionally in their fully deprotonated enol forms. Due to the formation of bridge, the V-O(methoxy) bond in the dimeric complexes is lengthened to such an extent that it becomes equal in length with the V-O(phenolate) bond in 3A and even longer in 1A and 2A, which is unprecedented. The H-1 NMR spectra of the complexes 1A-3A in CDCl3 solution, indicates that these dimeric complexes are converted appreciably into their respective monomeric form. Complexes are electro-active displaying one quasi-reversible reduction peak near +0.25 V versus SCE in CH2Cl2 solution. The E-1/2 values of the complexes show linear relationship with the Hammett parameter (sigma) of the substituents. All these VO3+-complexes are converted to the corresponding complexes with V2O34+ motif simply on refluxing them in acetone and to the complexes with VO2+ motif on reaction with 2 KOH in methanol. (C) 2008 Elsevier Ltd. All rights reserved.

Electrochemical deposition of praseodymium oxide on tin-doped indium oxide as a thin sensing film

Fabrication of a thin praseodymium oxide film is of great technological interest in sensor, semiconducting, and ceramic industries. It is shown for the first time that an ultrathin layer of praseodymium oxide can be deposited on tin-doped indium oxide surface (ITO) by applying a negative sweeping voltage (cathodic electrodeposition) to the aqueous solution containing Pr(NO3)(3) and H2O2 using cyclic voltammetry, followed by annealing the film at 500 S C for 1 h. X-ray diffraction suggested that the predominant phase of the film is Pr6O11 and atomic force microscopy and scanning electron microscopy characterizations indicated that this film is assembled with a monolayer coverage of spherical praseodymium oxide nanoparticles packed closely on the ITO surface. AC impedance measurements of the thin Pr6O11 film on ITO also revealed that the composite material displays a much higher electrical conductivity compared to the pure ITO. As a result, the material could suitably be used as a new chemical sensor. (c) 2006 The Electrochemical Society.

Layer-by-layer deposition of praseodymium oxide on tin-doped indium oxide (ITO) surface

Praseodymium oxide as a thin film of controllable layer is known to display many unique physiochemical properties, which can be useful to ceramic, semiconductive and sensor industries. Here in this short paper, we describe a new chemical method of depositing praseodymium oxide on tin-doped indium oxide (ITO) surface using a layer-by-layer approach. The process is carried out by dipping the ITO in solutions of adsorbable polycationic chitosan and alkaline praseodymium hydroxide Pr(OH)(3) alternatively in order to build up the well-defined multi-layers. XRD suggests that the predominant form of the oxide is Pr6O11, obtained after heat treatment of the deposited ITO in static air at 500 degrees C. Microscopic studies including AFM, TEM and SEM indicate that the deposited oxide particles are uniform in size and shape (cylindrical), mesoporous and the thickness of the film can be controlled. AC impedance measurements of the deposited materials also reveal that the oxide layers display a high electrical conductivity hence suitable for sensor uses. (c) 2006 Elsevier B.V. All rights reserved.

Templated synthesis of the novel layered silver-antimony Sulfides [H3NCH2CH2NH2][Ag2SbS3] and [H3NCH2CH2NH2](2)[Ag5Sb3S8]

Two new silver-antimony sulfides, [C2H9N2][Ag2SbS3] (1) and [C2H9N2](2)[Ag5Sb3S8] (2), have been prepared solvothermally in the presence of ethylenediamine and characterized by single-crystal X-ray diffraction, thermogravimetry, and elemental analysis. Compound 1 crystallizes in the space group Pn (a = 6.1781(1) Angstrom, b =11.9491(3) Angstrom, c = 6.9239(2) Angstrom, =111.164(1)degrees) and 2 in the space group Pm (a = 6.2215(2) Angstrom, b = 15.7707(7) Angstrom, c = 11.6478(5) Angstrom, beta = 92.645(2)degrees). The structure of 1 consists of chains of fused five-membered Ag2SbS2 rings linked to form layers, between which the template molecules reside. Compound 2 contains honeycomb-like sheets of fused silver-antimony-sulfide six-membered rings linked to form double layers. The idealized structure can be considered to be an ordered defect derivative of that of lithium bismuthide, Li3Bi, and represents a new solid-state structure type.

Investigation of tin-based alternatives for cadmium in optoelectronic thin-films materials

Increasing legislation has steadily been introduced throughout the world to restrict the use of heavy metals, particularly cadmium (Cd) and lead (Pb) in high temperature pigments, ceramics, and optoelectronic material applications. Removal of cadmium from thin-film optical and semiconductor device applications has been hampered by the absence of viable alternatives that exhibit similar properties with stability and durability. We describe a range of tin-based compounds that have been deposited and characterized in terms of their optical and mechanical properties and compare them with existing cadmium-based films that currently find widespread use in the optoelectronic and semiconductor industries. (c) 2008 Optical Society of America.

A simplified, high-yield synthesis, and crystal structure of [tris{bis(2,4,6-triisopropylphenyl)tin}]

The species [{Sn(C2H2iPr3-2,4,6)2}3] has been obtained in a simple, essentially quantitative, synthesis from SnCl2 and ArLi in diethyl ether at low temperature. The crystal structure analysis confirms the trimeric nature of the molecular units but reveals some unusual features. The crystal contains the unusual feature of an asymmetric unit that consists of three units of [{SnAr2}3] in P21/c; the molecular unit is a scalene triangle, showing high consistency between the three molecules, in contrast to analogous trimeric species of silicon or germanium. The SnSn bonds are lengthened (average value 2.942 Å) owing to steric crowding.

Synthesis of the first-membered ring compound containing three tin atoms and one oxygen. The crystal structure of the species [O{Sn(C6H3Et2-2,6)2}3]

Aerial oxidation of the novel homocyclic tetratin species [{SnAr2}3SnArBr] (1) [1] (Ar  C6H3Et2-2,6) affords the tritin heterocycle [O{Sn(C6H3Et2-2,6)2}3] (2), which has been crystallographically characterised; 2 is the first reported oxatristannacyclobutane, and the first heterocyclic tin species having both tintin and tinheteroatom bonds.

Tin–osmium cluster formation with a monomeric tin(II) alkyl: the formation, crystal structure and reactivity of [Os3(µ-H)SnR(CO)10], a formal stannyne complex of the osmium triangle {R = C(SiMe3)2C5H4N-2}

The monomeric tin(II) species SnR2{R = C(SiMe3)2C5H4N-2} reacts with [Os3(H)2(CO)10] in hexane to give [Os3(µ-H)SnR(CO)10]1 quantitatively; 1 is the first formal stannyne complex of the triosmium nucleus, in which the picoline nitrogen is coordinated to the tin atom, and which is itself also reactive, being a potential precursor to high nuclearity SnOs clusters.