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                <title xml:lang="en">Alkali-metal ion coordination in uranyl(VI) poly- peroxide complexes in solution. Part 1: the Li&lt;sup&gt;+&lt;/sup&gt;, Na&lt;sup&gt;+&lt;/sup&gt; and K&lt;sup&gt;+&lt;/sup&gt; – peroxide–hydroxide systems</title>
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              <p>The alkali metal ions Li&lt;sup&gt;+&lt;/sup&gt;, Na&lt;sup&gt;+&lt;/sup&gt; and K&lt;sup&gt;+&lt;/sup&gt; have a profound influence on the stoichiometry of the complexes formed in uranyl(VI)–peroxide–hydroxide systems, presumably as a result of a templating effect, resulting in the formation of two complexes, M[(UO&lt;sub&gt;2&lt;/sub&gt;)(O&lt;sub&gt;2&lt;/sub&gt;)(OH)]&lt;sup&gt;2−&lt;/sup&gt; where the uranyl units are linked by one peroxide bridge, &amp;mu;-&amp;eta;&lt;sub&gt;2&lt;/sub&gt;-&amp;eta;&lt;sub&gt;2&lt;/sub&gt;, with the second peroxide coordinated “end-on”, &amp;eta;&lt;sub&gt;2&lt;/sub&gt;, to one of the uranyl groups, and M[(UO&lt;sub&gt;2&lt;/sub&gt;)(O&lt;sub&gt;2&lt;/sub&gt;)(OH)]&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;3-&lt;/sup&gt;, with a four-membered ring of uranyl ions linked by &amp;mu;-&amp;eta;&lt;sub&gt;2&lt;/sub&gt;-&amp;eta;&lt;sub&gt;2&lt;/sub&gt; peroxide bridges. The stoichiometry and equilibrium constants for the reactions: M&lt;sup&gt;+&lt;/sup&gt; + 2UO&lt;sub&gt;2&lt;/sub&gt;&lt;sup&gt;2+&lt;/sup&gt; + 2HO&lt;sub&gt;2&lt;/sub&gt;&lt;sup&gt;−&lt;/sup&gt; + 2H&lt;sub&gt;2&lt;/sub&gt;O → M[(UO&lt;sub&gt;2&lt;/sub&gt;)(O&lt;sub&gt;2&lt;/sub&gt;)(OH)]&lt;sub&gt;2&lt;/sub&gt;&lt;sup&gt;−&lt;/sup&gt; + 4H&lt;sup&gt;+&lt;/sup&gt; (1) and M&lt;sup&gt;+&lt;/sup&gt; + 4UO&lt;sub&gt;2&lt;/sub&gt;2&lt;sup&gt;+&lt;/sup&gt; + 4HO&lt;sub&gt;2&lt;/sub&gt;&lt;sup&gt;−&lt;/sup&gt; + 4H&lt;sub&gt;2&lt;/sub&gt;O → M[(UO&lt;sub&gt;2&lt;/sub&gt;)(O&lt;sub&gt;2&lt;/sub&gt;)(OH)]&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;3−&lt;/sup&gt; + 8H&lt;sup&gt;+&lt;/sup&gt; (2) have been measured at 25 °C in 0.10 M (tetramethyl ammonium/M+)NO&lt;sub&gt;3&lt;/sub&gt; ionic media using reaction calorimetry. Both reactions are strongly enthalpy driven with large negative entropies of reaction; the observation that &amp;Delta;H(2) ≈ 2&amp;Delta;H(1) suggests that the enthalpy of reaction is approximately the same when peroxide is added in bridging and “end-on” positions. The thermodynamic driving force in the reactions is the formation of strong peroxide bridges and the role of M&lt;sup&gt;+&lt;/sup&gt; cations is to provide a pathway with a low activation barrier between the reactants and in this way “guide” them to form peroxide bridged complexes; they play a similar role as in the synthesis of crown-ethers. Quantum chemical (QC) methods were used to determine the structure of the complexes, and to demonstrate how the size of the M&lt;sup&gt;+&lt;/sup&gt;-ions affects their coordination geometry. There are several isomers of Na[(UO&lt;sub&gt;2&lt;/sub&gt;)(O&lt;sub&gt;2&lt;/sub&gt;)(OH)]&lt;sub&gt;2&lt;/sub&gt;&lt;sup&gt;-&lt;/sup&gt; and QC energy calculations show that the ones with a peroxide bridge are substantially more stable than the ones with hydroxide bridges. There are isomers with different coordination sites for Na&lt;sup&gt;+&lt;/sup&gt; and the one with coordination to the peroxide bridge and two uranyl oxygen atoms is the most stable one.</p>
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