H. Mercier, G. Schrobilgen
Jan 20, 1993
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0
Influential Citations
28
Citations
Journal
Inorganic Chemistry
Abstract
The synthesis of TcO[sub 2]F[sub 3], which is reported for the first time, was accomplished by the reaction of XeF[sub 6] and Tc[sub 2]O[sub 7] in a 3:1 molar ratio in anhydrous HF solution. Technetium(VII) dioxotrifluoride is yellow (mp 200 [plus minus] 1[degree]C) and crystallized in the triclinic system, space group P[bar 1], with a = 7.774 (3) [Angstrom], b = 7.797 (1) [Angstrom], c = 11.602 (3) [Angstrom], [alpha] = 89.41 (2)[degrees], [beta] = 88.63 (3)[degrees], [gamma] = 84.32 (2)[degrees], V = 699.6 (3) [Angstrom][sup 3], D[sub calc] = 3.551 g cm[sup [minus]3] for Z = 8 from HF solutions containing excess XeF[sub 6]. The structure consists of open chains of fluorine bridged TcO[sub 2]F[sub 4] units in which the bridge fluorines (F[sub b]) are trans to the oxygens and the light atoms surrounding technetium form near-undistorted octahedra in which the technetium atoms are displaced toward the oxygen atom in the [F[sub b],F[sub b],O,O] plane: terminal Tc-F, 1.834 (7) [Angstrom]; bridging Tc---F, 2.080 (5) [Angstrom]; Tc-O, 1.646 (9) [Angstrom]; Tc---F---Tc, 148.8 (3)[degrees]. The Raman spectrum of the polymeric cis-TcO[sub 2]F[sub 4] unit has been assigned under C[sub 2v] point symmetry and exhibits only weak vibrational coupling in the unitmore » cell. 50 refs., 4 figs., 4 tabs.« less