Chlorine complexes bridge systems

The precise structural role played by the water molecules in these cements is not clear. In the zinc oxychloride cement, water is known to be thermally labile. The 1 1 2 phase will lose half of its constituent water at about 230 °C, and the 4 1 5 phase will lose water at approximately 160 C to yield a mixture of zinc oxide and the 1 1 2 phase. Water clearly occurs in these cements as discrete molecules, which presumably coordinate to the metal ions in the cements in the way described previously. However, the possible complexities of structure for these systems, which may include chlorine atoms in bridging positions between pairs of metal atoms, make it impossible to suggest with any degree of confidence which chemical species or what structural units are likely to be present in such cements. One is left with the rather inadequate chemical descriptions of the phases used in even the relatively recent original literature on these materials, from which no clear information on the role of water can be deduced. 

Often, with precipitation reactions the starting materials are limited to whatever salts are soluble in the solvent of choice. For water systems this is often limited to metal salts of halides, nitrates, and some sulfates and phosphates. Halides, in particular chlorides, have a pronounced effect on precipitation reactions. Chlorine is able to form bridged complexes much like the hydroxides or oxides of the desired compounds. In addition, acidic environments make possible the oxidation of chloride to chlorine gas, which can further complicate the synthesis. Sulfates and phosphates are typically easier to work with since they do not have the complicated redox behavior of the halides, but they typically have reduced solubilities. Nitrates, although they do not have the solubility concerns of sulfates and phosphates, do have redox complications, which typically result in oxidation of cations. So, the anion, which is expected to act solely as a spectator, in many cases is actually acting as a catalyst. 

The IR spectra suggest that the uranium is indeed bound to the ring oxygens. The asymmetric stretch frequency associated with the CH2CH2OCH2CH2 system shifts to lower frequency by about 20-40 cm i in the complexes 81). It has been suggested that the polynuclear complexes are chlorine bridged, 4. 

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