The preparation of ReOCl,, by photodecomposition of ReOC1, and other methods, is described.FOLLOWING the preparation of the first complexes of ReOCl,,' many reports of further complexes appeared,, but so far there has been no report of the successful preparation of ReOCl,. Edwards et aZ.* recently reported a number of methods which were used in attempts to prepare ReOCl,, but which were unsuccessful. We have independently used these same methods, also with no success, but we have found three methods for the successful preparation of ReOCl,. We have also shown that ReOCl, exists in at least two different solid forms.The first two methods of preparation involve the reaction of Re& with ReO, or ReC1, with ReO, a t 300' in sealed tubes. These reactions are not clean; depending on the ratio of the reactants varying amounts of ReO,Cl, ReOCl,, Re,Cl,, and even rhenium metal are produced, and ReOCl, is rarely the major product. However, it is possible to separate ReOCl, from the other products by careful trap to trap distillation in vacuo, and most of our work has been done on ReOCI, produced by these methods.More recently we have discovered a third, and far more satisfactory way of producing ReOCI, by the photodecom-
The preparation and some physical and chemical properties of ReOCI, are described.On dCcrit la prkparation ainsi que quelques propri Can. J Chem . 51. 828 (1973) Introduction Until recently only two oxochlorides of rhenium have been clearly established, namely ReOCl, and Re03Cl (1). Very recently there have been reports of ReOCI, (2) and the mixed complexes Re03Cl-ReOCl, (3) and Re,03C1,-(ReO,Cl), (4). We now report the existence of yet another simple oxochloride, namely oxodichlororhenium(IV), ReOCI,. ExperimentsRhenium and chlorine analyses were performed by the neutron activation method described previously (5). Infrared spectra were recorded for solid samples ground into a mull with Nujol. The Nujol had been dried by refluxing with phosphorus pentoxide followed by vacuum distillation. The mull samples were mounted between potassium bromide plates and spectra were recorded on Perkin-Elmer 337, 521, and 301 spectrometers. Raman emission was excited by 10 mW of radiation from a He-Ne laser 0,6328 A), and spectra were recorded with a Coderg PHO double monochromator with photoelectric detection. X-Ray diffraction photographs of powdered samples were recorded on a Debye-Scherrer camera. Samples were sealed inside fused quartz tubes and nickel-filtered CuKcc radiation was used for recording the photographs. Line intensities were measured from the photographs with a Joyce-Loebl microdensitometer. ReOC12 was prepared by a number of different chemical reactions. Typical reaction conditions are described below unless changes in the conditions made significant differences in the distribution of products, in which case different runs are described. Analysi~ and Identification of Prod~lctsFor qualitative identification of products only infrared spectroscopy (volatile materials) or X-ray diffraction (involatile n~aterials) was used. Combination of these techniques with quantitative analysis (see below) applied to pure and known "impure" samples (i.e. mixtures of known composition) has shown that infrared spectroscopy could identify as little as 5% of an impurity (and in many cases < 1%) while X-ray diffraction could detect as little as 5% of impurity in a single substance and 10% in a ' T o whom correspondence should be addressed.CtCs physiques et chimiques de ReOC1,.[Traduit par le journal] mixture of two compounds. For X-ray diffraction it is possible that large quantities of an amorphous product were present but we have no other evidence for this in any of our experiments. For each type of reaction reported below many runs were made (typically 5-10) and in most runs attempts were made not only to separate volatile and involatile products, but to separate the products into individual components. This was hard to do for volatile products, but for involatile products was achieved by hand-picking crystals. Parts of both volatile and involatile samples were examined by X-ray and infrared techniques to confirm that only the expected products were present. For quantitative analysis of a reaction, the nature of the products ...
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