APPLICATIONS OF THE SALT/MOLECULE REACTION TECHNIQUE TO OXIDE SALTS: INFRARED SPECTRA OF THE $Tl_{2} ^{+}CO_{3}^{=}$ AND $Tl_{2} ^{+}SO_{3}^{=}$ TRIPLE IONS
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Date
1982
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Ohio State University
Abstract
Application of the salt/molecule reaction technique, developed several years ago for anion formation in inert matrices through halide ion transfer, has been extended to oxide salt reactions. Thallium (I) oxide, $Tl_{2}O$, has been vaporized and codeposited with samples of $Ar/CO_{2}$ and its isotopic counterparts at a variety of dilutions. A series of product bands were observed which can be assigned to $CO_{3}^{=}$ anion in the $Tl_{2} ^{+}CO_{3}^{=}$ triple ion. The symmetry of the carbonate anion is lowered from $D_{3h}$ as a consequence of the two metal cations. Moreover, the spectra and assignments are supported by the direct vaporization of alkali metal carbonate salts into inert matrices. This technique has also been applied to synthesize the $SO_{3}^{=}$ anion through the reaction of $Tl_{2}O$ with $SO_{2}$ in inert matrices. The product bands which have been observed, to date, seem to indicate that the $Tl^{+}$ cations are in contact with both sulfur and oxygen atoms. These studies will continue for isolation of highly reactive oxyanions which cannot be formed and stabilized at room temperature.