Room temperature syntheses of MnF3, MnF4 and hexafluoromanganete(IV) salts of alkali cations

Elemental fluorine oxidises MnF2 in anhydrous hydrogen fluoride (aHF) as a solvent at room temperature yielding pure MnF3. In the presence of a UV source, MnF2 is completely oxidised by photodissociated F2 in aHF to MnF4. Photochemical reactions with elemental fluorine on 2AF (A=Li, Na, K, Rb, Cs)/MnF2 mixtures in aHF as a solvent at room temperature yield pure A2MnF6 compounds. An attempt to prepare CsMnVF6 by oxidation of MnF2 with UV-irradiated F2 in the presence of an equimolar amount of CsF in aHF failed. The final products of these reactions were mixtures of MnF4 and Cs2MnF6. Described syntheses represent milder approaches for the preparation of larger amounts of MnF3, MnF4, and A2MnF6 on a gram scale.