ABSTRACT: Experiments on the preparation of the new mixed cations XeF5M(AF6)3 (M = Cu, Ni; A = Cr, Nb, Ta, Ru, Rh, Re, Os, Ir, Pt, Au, As), XeF5M(SbF6)3 (M = Sn, Pb), and XeF5M(BF4)x(SbF6)3-x (x = 1, 2, 3; M = Co, Mn, Ni, Zn) salts were successful only in the preparation of XeF5Ni(AsF6)3. In other cases, mixtures of different products, mostly XeF5AF6 and XeF5A2F11 salts, were obtained. The crystal structures of XeF5Ni(AsF6)3, XeF5TaF6, XeF5RhF6, XeF5IrF6, XeF5Nb2F11