• (R=H) [212784‐73‐1] C₃₆H₃₆N₈Cl₄O₈Ru₂ (MW 1052.68)

  InChI = 1S/2C21H24N4.2ClHO4.2ClH.2Ru/c2*1‐16‐4‐7‐19(22‐10‐16)13‐25(14‐20‐8‐5‐17(2)11‐23‐20)15‐21‐9‐6‐18(3)12‐24‐21;2*2‐1(3,4)5;;;;/h2*4‐12H,13‐15H2,1‐3H3;2*(H,2,3,4,5);2*1H;;/q;;;;;;2*+2/p‐4

  InChIKey = CGIXVWKDNAQNPK‐UHFFFAOYSA‐J

• (R=CH₃) [212784‐75‐3]] C₄₂H₄₈N₈Cl₄O₈Ru₂ (MW 1136.84)

  InChI = 1/2C21H24N4.2ClHO4.2ClH.2Ru/c2*1‐16‐4‐7‐19(22‐10‐16)13‐25(14‐20‐8‐5‐17(2)11‐23‐20)15‐21‐9‐6‐18(3)12‐24‐21;2*2‐1(3,4)5;;;;/h2*4‐12H,13‐15H2,1‐3H3;2*(H,2,3,4,5);2*1H;;/q;;;;;;2*+2/p‐4/f2C21H24N4.2ClO4.2Cl.2Ru/h;;;;2*1h;;/q;;4*‐1;2m/r2C21H24N4.2ClHO4.2

  InChIKey = CGIXVWKDNAQNPK‐FCFTURCTCS

(homogeneous catalysts for hydroxylation and ketonization of alkanes with alkyl hydroperoxides,¹ allylic oxidation, epoxidation of alkenes, sulfoxidation of sulfides, and co‐oxygenation of alkanes with dioxygen²)

Physical data: redox potential (vs. Fc/Fc⁺ as 0 V in CH₃CN/0.1 M TBAP at room temperature); 0.22 V (Ru^IIRu^II/Ru^IIRu^III) and 0.71 V (Ru^IIRu^III/Ru^IIIRu^III) for R = H, 0.17 V (Ru^IIRu^II/Ru^IIRu^III) and 0.66 V (Ru^IIRu^III/Ru^IIIRu^III) for R = CH₃.

Solubility: soluble in CH₃CN, acetone, MeOH, CH₂Cl₂; insoluble in hydrocarbons and aromatics.

Form Supplied in: orange solids; not commercially available.

Preparation Methods: for R = H; to a degassed solution of TPA•3HClO₄ (0.68 g, 1.15 mmol) and NEt₃ (0.58 g, 5.73 mmol) in CH₃OH (20 mL), was added a solution of RuCl₃•3 H₂O (0.30 g, 1.15 mmol) in CH₃OH (20 mL) under N₂ via a cannula. The mixture was heated at reflux for 8 h and the brown precipitate was collected by filtration. The brown powder was washed with ether and dissolved into CH₃CN. Insoluble materials were removed by filtration through a Celite column (2 cm × 5 cm) to obtain a reddish orange solution. The solvent was removed via rotatory evaporator, and the resultant orange powder was washed well with ether then dried.

For R = CH₃; a mixture including 5‐Me₃‐TPA (0.665 g, 2 mmol), NEt₃ (1.012 g, 10 mmol), and NaClO₄ (1.22 g, 10 mmol) under N₂ was added via a cannula to a degassed solution of RuCl₃•3H₂O (0.523 g, 2 mmol) in CH₃OH (20 mL). The mixture was heated at reflux for 12 h and then filtered to obtain a yellow‐brown powder. The crude product was dissolved into CH₃CN and filtered through a Celite 535 column to afford a reddish orange solution. The orange powder, obtained by removing the CH₃CN, was washed with ether and dried.

Purification: if necessary, recrystallization from CH₃CN or CH₃OH gives single crystals of these compounds.

Handling, Storage and precaution: perchlorate salts of metal compounds with organic ligands are potentially explosive. Great care should be required. Air stable.