[9][10] Other preparations of MnF4 include the fluorination of MnF2 with krypton difluoride,[11] or with F2 in liquid hydrogen fluoride solution under ultraviolet light.

[12] Manganese tetrafluoride has also been prepared (but not isolated) in an acid–base reaction between antimony pentafluoride and K2MnF6 as part of a chemical synthesis of elemental fluorine.

[17] The equilibrium pressure of fluorine above MnF4 at room temperature has been estimated at 10−4 Pa (10−9 bar), and the enthalpy change of reaction at +44(8) kJ mol−1.

[2] Reaction with alkali metal fluorides or concentrated hydrofluoric acid gives the yellow hexafluoromanganate(IV) anion [MnF6]2−.

Further impurities, such as iron, nickel, gallium and tungsten compounds, can be introduced if unreacted fluorine is recycled.

[23][24] The pentafluoromanganate(1−) salts of potassium, rubidium and caesium, MMnF5, can be prepared by fluorination of MMnF3 or by the reaction of [MnF4(py)(H2O)] with MF.