Complex 1 was readily synthesized via UV photoirradiation of a methanol solution of [Ru(Cp)(C6H6)]B(CN)4 (Figs. ). After 1 h of irradiation, pale yellow benzene-solvate crystals (1•0.5C6H6) formed on the walls of the reaction vessel, yielding 58% (Fig. ). The photoreaction induced the dissociation of the benzene ligand, followed by the coordination of the B(CN)4 -anion to the Ru center, with the released benzene subsequently incorporated into the crystal as a solvate molecule. Alternatively, complex 1 can be synthesized via the reaction of [Ru(Cp)(MeCN)3]PF6 with KB(CN)4 in acetonitrile, though this method requires additional workup and purification, yielding 64% (Figs. ).