Controlled chemistry of Moisture Sensitive Reagents in Ionic Liquids

Many reactions involving phosphorus reagents require highly anhydrous and inert conditions for their successful implementation. In particular, the use of PCl3 and its derivatives for synthesis is often hampered by the inherent sensitivity of the materials themselves. Ionic liquids are emerging as green alternative solvents for a range of processes, and in particular have proven to be excellent media for highly sensitive phosphorus reagents without the need for anhydrous or inert conditions. Herein, we report the use of ionic liquids as both storage and reaction media which allows difficult and sensitive chemistry to be achieved in a more accessible manner.

Temporal variation in the water chemistry of northern Victoria Land lakes (Antarctica)

Concentrations of major ions, silicate and nutrients (total N and P) were measured in samples of surface water from 28 lakes in ice-free areas of northern Victoria Land (East Antarctica). Sixteen lakes were sampled during austral summers 2001/02, 2003/04, 2004/05 and 2005/06 to assess temporal variation in water chemistry. Although samples showed a wide range in ion concentrations, their composition mainly reflected that of seawater. In general, as the distance from the sea increased, the input of elements from the marine environment (through aerosols and seabirds) decreased and there was an increase in nitrate and sulfate concentrations. Antarctic lakes lack outflows and during the austral summer the melting and/or ablation of ice cover, water evaporation and leaching processes in dry soils determine a progressive increase in water ion concentrations. During the five-year monitoring survey, no statistically significant variation in the water chemistry were detected, except for a slight (hardly significant) increase in TN concentrations. However, Canonical Correspondence Analysis (CCA) indicated that other factors besides distance from the sea, the presence of nesting seabirds, the sampling time and percentage of ice cover affect the composition of water in Antarctic cold desert environments.

The synthesis and chemistry of formylphosphonate

New methods of synthesis and reactions of formylphosphonate have been investigated. Attempts to deprotect the corresponding diethyl acetal with Ti-IV halides led instead to the formation of halo(ethoxy)methylphosphonates which undergo substitution reactions with a wide range of nucleophiles. The products of reactions of formylphosphonate with bifunctional nucleophiles are determined in most cases by Baldwin's Roles, while the imines derived from formylphosphonate undergo Diels-Alder reactions only in those cases which carry a strongly electron-withdrawing N-substituent.

Photodissociation and chemistry of N2 in the circumstellar envelope of carbon-rich AGB stars

The envelopes of AGB stars are irradiated externally by ultraviolet photons; hence, the chemistry is sensitive to the photodissociation of N$_2$ and CO, which are major reservoirs of nitrogen and carbon, respectively. The photodissociation of N$_2$ has recently been quantified by laboratory and theoretical studies. Improvements have also been made for CO photodissociation. For the first time, we use accurate N$_2$ and CO photodissociation rates and shielding functions in a model of the circumstellar envelope of the carbon-rich AGB star, IRC +10216. We use a state-of-the-art chemical model of an AGB envelope, the latest CO and N$_2$ photodissociation data, and a new method for implementing molecular shielding functions in full spherical geometry with isotropic incident radiation. We compare computed column densities and radial distributions of molecules with observations. The transition of N$_2$ $\to$ N (also, CO $\to$ C $\to$ C$^+$) is shifted towards the outer envelope relative to previous models. This leads to different column densities and radial distributions of N-bearing species, especially those species whose formation/destruction processes largely depend on the availability of atomic or molecular nitrogen, for example, C$_n$N ($n$=1, 3, 5), C$_n$N$^-$ ($n$=1, 3, 5), HC$_n$N ($n$=1, 3, 5, 7, 9), H$_2$CN and CH$_2$CN. The chemistry of many species is directly or indirectly affected by the photodissociation of N$_2$ and CO, especially in the outer shell of AGB stars where photodissociation is important. Thus, it is important to include N$_2$ and CO shielding in astrochemical models of AGB envelopes and other irradiated environments. In general, while differences remain between our model of IRC +10216 and the observed molecular column densities, better agreement is found between the calculated and observed radii of peak abundance.