Toxicity organometallics

It will be clear from the above examples that hydride-forming elements especially are often subjected to such speciation studies. There are, of course, good reasons for this. These are the very elements which tend to form toxic organometallic compounds, and they are elements which may be determined with excellent sensitivity. Moreover, interferences are not usually a problem following a separation process. 

The latter example points out the potential of the technique as a screening method for the identification of toxic organometallic compounds, for example, in pesticide residue analysis. With an initial screening of total Sn by ICP-MS in a survey on cyhexatin (an organotin acaricide), a limited number of suspect fruit samples (three out of 72) were identified and then submitted to confirmatory analysis with a GC-MS method [85]. This approach resulted in a 30 percent reduction of the survey cost in terms of staff hours. 

Non-oxide ceramic nanomaterials, such as carbides, nitrides, borides, phosphides and silicides, have received considerable attention due to their potential applications in electronics, optics, catalysis, and magnetic storage. In contrast with the traditional processes, such as solid state reactions, CVD, MOCVD and PVD, which involve using high temperatures, toxic organometallic precursors, or complicated reactions and posttreatments, solvothermal method is a low temperature route to these materials with controlled shapes and sizes. 

For instance, in the last decade synthesis of poly(ester-alt-ether) was intensively studied. A common enzyme used in these syntheses is CALB. Polymerization of l,5-dioxepan-2-one (DXO) was performed by enzyme-catalyzed ROP in order to avoid contamination of product polymers by toxic organometallic catalysts [92], High molecular weight of poly(DXO) was obtained (Mn = 56000 Mw = 112000, 97% yield) at 60 °C for 4h. The polymerization had the characteristics of a living polymerization, as indicated by the linearity of plots between M and monomer conversion, meaning that the product molecular weight could be controlled by the stoichiometry of the reactants. Similarly, Nishida et al. [91] carried out enzymatic ROP of l,4-dioxan-2-one at 60 °C catalyzed by Novozym 435 that resulted in a polymer with Mw = 41000 in 77% yield. 

Dmitriev, M. T., Bykhovskii, M. Ya., Brande, A., Chromatoatomic Absorption Measurement of Toxic Organometallic Compounds in Hygienic Research Studies, Gig. Sanit. 1983 No. 12, pp. 43/6. 

Huang G, Bai Z, Dai S, Xie Q (1993) Accumulation and toxic effects of organometallic compounds on algae. Applied Organometallic Chemistry, 7 265-271. 

Mercury, tin, lead, arsenic, and antimony form toxic lipophilic organometallic compounds, which have a potential for bioaccumulation/bioconcentration in food chains. Apart from anthropogenic organometallic compounds, methyl derivatives of mercury and arsenic are biosynthesized from inorganic precursors in the natural environment. 

This concept meshes with another important environmental issue solvents for organic reactions. The use of chlorinated hydrocarbon solvents, traditionally the solvent of choice for a wide variety of organic reactions, has been severely curtailed. In fact, so many of the solvents favoured by organic chemists have been blacklisted that the whole question of solvents requires rethinking. The best solvent is no solvent and if a solvent (diluent) is needed then water is preferred. Water is non-toxic, non-inflammable, abundantly available, and inexpensive. Moreover, owing to its highly polar character, one can expect novel reactivities and selectivities for organometallic catalysis in water. 

Reacts with many metals to give hydrogen, sometimes violently. With non-metals pyrophoric hydrides may result. Frequently initiates explosive reactions between other substances. Violent reactions with many non-metal and some metal halides and oxyhalides, also with many organometallic compounds. Many metal nonmetal-lides produce toxic, flammable or pyrophoric gases on contact with diprotium monoxide. 

The environmental impact of tin is appreciable, as it is one of the three most enriched metals—only lead and tellurium precede—in the atmospheric particular matter, as compared with the abundance of the element in the earth crust (2.2 ppm). Tin releases to the environment can be methylated by aquatic organisms, yielding organometallic species of toxicity comparable to that of methylated mercury5. 

Kaise, T. and S. Fukui. 1992. The chemical form and acute toxicity of arsenic compounds in marine organisms. Appl. Organometall. Chem. 6 155-160. 

Both of these types of organometallics have the disadvantages of difficulties in preparation and extreme toxicity. Their major advantage is that they provide a controlled reaction, allowing a single halogen of the phosphorus halide to be displaced, leaving the others untouched. 

---