Long-Lived Radical Cation Salts Obtained by Interaction of Monocyclic Arenes with Niobium and Tantalum Pentahalides at Room Temperature: EPR and DFT Studies.

The 1:3 reactions of the alkoxy arenes 1,4-(MeO)2C6H4 and 1,4-F2-2,5-(MeO)2C6H2 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)2C6H4][Ta2F11] ( 2 a) and [1,4-F2-2,5-(MeO)2C6H2][Ta2F11] ( 2 b), respectively. The non-alkoxy-substituted [arene][M2X11] [M=Ta, X=F: arene=C6H5Me ( 2 c), 1,4-C6H4Me2 ( 2 d), C6H5F ( 2 e), C6H5NO2 ( 2 f); M=Nb, X=F: arene=C6H5Me ( 4 a), 1,4-C6H4Me2 ( 4 b), C6H5F ( 4 c), C6H5NO2 ( 4 d); M=Ta, X=Cl: arene=1,4-C6H4Me2 ( 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 MIV 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)2C6H2 with AgNbF6 (in CH2Cl2) and 1,4-(MeO)2C6H4 with SbF5. [ABSTRACT FROM AUTHOR]