A convenient one-step synthesis for [Mn(CO)(6)](+) salts has been developed. The method involves the one-electron oxidation of Mn-2(CO)lo by protons in solutions of Lewis acids (BF3, (CF3)(3)BCO) and anhydrous HF. The molecular structure of [Mn(CO)(6))[BF4]center dot SO2 was determined by single-crystal X-ray diffraction. Crystal data: orthorhombic, space group Cmc2(1); a = 8.7001(2) angstrom, b = 11.8497(3) angstrom, and c = 11.7437(3) angstrom; Z = 4; R1 = 0.0320 and wR2 14 = 0. 1106. The structural, NMR, and vibrational spectroscopic properties of [Mn(CO)(6)](+) fit perfectly with those of the isoelectronic species [V(CO)(6)](-), Cr(CO)(6), and [Fe(CO)(6)](2+).