The 1:3 reactions of the alkoxy arenes 1,4-(MeO)2 C6 H4 and 1,4-F2 -2,5-(MeO)2 C6 H2 with TaF5 in chloroform at 40-50 °C resulted in formation in about 35 % yield of the long-lived radical cation salts [1,4-(MeO)2 C6 H4 ][Ta2 F11 ] (2 a) and [1,4-F2 -2,5-(MeO)2 C6 H2 ][Ta2 F11 ] (2 b), respectively. The non-alkoxy-substituted [arene][M2 X11 ] [M=Ta, X=F: arene=C6 H5 Me (2 c), 1,4-C6 H4 Me2 (2 d), C6 H5 F (2 e), C6 H5 NO2 (2 f); M=Nb, X=F: arene=C6 H5 Me (4 a), 1,4-C6 H4 Me2 (4 b), C6 H5 F (4 c), C6 H5 NO2 (4 d); M=Ta, X=Cl: arene=1,4-C6 H4 Me2 (5)] were obtained from the 3:1 reactions of MX5 with the appropriate arene in chloroform at temperatures in the range 40-90 °C. Compounds 2-5 were detected by EPR spectroscopy (in CHCl3 ) at room temperature, and their gas-phase structures were optimized by DFT calculations. Formation of the M(IV) species [MX4 (NCMe)2 ] [M=Ta, X=F (3 a); M=Nb, X=F (3 b); M=Ta, X=Cl (3 c)] was ascertained by EPR spectroscopy on solutions obtained by treatment of the reaction mixtures with acetonitrile. Non-selective reactions occurred upon combination of 1,4-F2 -2,5-(MeO)2 C6 H2 with AgNbF6 (in CH2 Cl2 ) and 1,4-(MeO)2 C6 H4 with SbF5 .