Direct reaction between [Cr(CO)₆] and arenes with ionic substituents affords the corresponding arene-chromium tricarbonyl complexes, [Cr(CO)₃(arene)], in only modest yield. In contrast, these complexes can be prepared in pure form in excellent yield from the reaction of [Cr(CO)₃(η⁶-C₆H₅CH₂Br)] with, for example, N-methylimidazole. The structures of [Cr(CO)₃(η⁶-C₆H₅CH₂MIM)]Br (MIM = 3-methylimidazolium), [Cr(CO)₃(η⁶-C₆H₅CH₂MMIM)]Br (MMIM = 2,3-dimethylimidazolium), and [Cr(CO)₃(η⁶-C₆H₅CH₂NMe₂(CH₃)₂OH)]Br have been established by X-ray diffraction analysis. Subsequent exchange of the bromide anion for Tf₂N^- affords new organometallic salts with melting points below 70 degrees C. Reaction of the bromide salts include tosylation of [Cr(CO)₃(η⁶-C₆H₅CH₂NMe₂(CH₃)₂OH)]Br to afford [Cr(CO)₃(η⁶-C₆H₅CH₂NMe₂(CH₂)₂OTs)]Br and the formation of the heterometallic carbene complex [Ru(η⁶-p-cymene)Cl₂{C₄H₅N₂CH₂Ph-η⁶-Cr(CO)₃}]. Both compounds were characterized in the solid state by X-ray diffraction.