Vapour density and vibrational spectra of MoOF4 and WOF4. The structure of crystalline WOF4

Abstract
Vapour density measurements on MoOF4 show this compound to be monomeric in the gas phase. Similar measurements on WOF4 show it to be essentially monomeric as a gas, although some association may occur at lower temperatures and higher pressures. Gas-phase Raman spectra of WOF4 are invariant in the range 200–600° and closely similar to those of the melt and solid. The results demonstrate that solid WOF4 is not principally an oxygen-bridged polymer. The spectra of MoOF4 are closely similar to those of WOF4 in all phases. Detailed studies of the gas-phase and matrix-isolated vibrational spectra of WOF4, including structure of gas phase i.r. bands and Raman depolarization data, strongly suggest that the molecule is a square pyramid with an apical oxygen.

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