Synthesis, crystal structure and spectroelectrochemistry of [(C5Me5Ru)2-η6,η6-chrysene]2+(O3SCF3−)2. Form RuII)-η6η6 -chrysene]O3SCF3

The binuclear complex [(C5Me5Ru)2-η6,η6 chrysene](O3SCF3) (1) was synthesized from [C5Me5Ru(CH3CN)3 1 is reduced by sodium naphthalene to the mixed valence complex [(C5Me5RuI [(C5Me5RuII)-η6,η6chrysene]O3SCF stable (coproportionation constant Kc = 2.57 × 105). Complex 2 is also formed by electrochemical reduction, as established by cyclovo + e ⇌ 2+. is reversible with E1 = − 1.37 V (vs. saturated calomel electrode), and at E2 = − 1.69 V a second, ir 2 shows g1 = 2.025, g2 = 2.009 and g3 = 1.998 (giso = 2.011). An intervalence absorption band is observed for 2 13C-NMR data are reported for 1. A dielectronic reduction of 1++ with two equivalents of sodium naphthalene affords the unstable diam η5-chrysene] (3) that probably has a cyclohexadienyl configuration configuration respect to the RuII-chrysene bonds. An X-ray crystal str centrosymmetric doubly charged cation in 1 each of the two Ru atoms has a sandwich-type coordination between a C5Me5 group and one of the t