Add time:07/27/2019         Source:sciencedirect.com

We report in this paper vibrational spectra (i) for selenium tetrafluoride in the vapour and solid phases, and isolated in inert-gas matrices, and (ii) for tellurium tetrafluoride in both the solid and matrix-isolated condition. The discrete SeF4 and TeF4 molecules have C2v symmetry, on the basis of which their fundamental frequencies are assigned; force constants, obtained by normal coordinate analysis, show the axial bonds to be weaker than the equatorial ones. Vibrational features arising from more-or-less strongly bonded oligomers, which are found in more concentrated matrices or on diffusion of the monomerio species, are consistent with bridging interactions involving only the axial M-F bonds, leaving the equatorial MF2 units largely unchanged. Likewise retained in the crystalline tetrafluorides, the equatorial unit of the MF4 molecule corresponds to relatively short terminal bonds in the polymeric aggregate, but, with respect to the isolated molecule, features characteristic of stretching fundamentals of the axial MF2 moieties are shifted to much lower frequency.

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