Triruthenium Dodecacarbonyl

Triruthenium dodecacarbonyl is the chemical compound with the formula Ru₃(CO)₁₂. Classified as metal carbonyl cluster, it is a dark orange-colored solid that is soluble in nonpolar organic solvents. The compound serves as a precursor to other organoruthenium compounds.

Structure and synthesis

The cluster has ''D_3h'' symmetry, consisting of an equilateral triangle of Ru atoms, each of which bears two axial and two equatorial CO ligands. The Ru-Ru distance is 284 pm. Os₃(CO)₁₂ has the same structure. In Fe₃(CO)₁₂, two CO ligands are bridging, resulting in C_2v symmetry. In solution, is fluxional as indicated by the observation of a single CO signal in the room temperature ¹³C NMR spectrum. The barrier is estimated at 20 kJ/mol

is prepared by treating solutions of ruthenium trichloride with carbon monoxide in the presence of a base. Dichlororuthenium tricarbonyl dimer is an intermediate. The stoichiometry of the reaction is uncertain, one possibility being the following:
:6 RuCl₃ + 33 CO + 18 CH₃OH → 2 Ru₃(CO)₁₂ + 9 CO(OCH₃)₂ + 18 HCl

Reactions

The chemical properties of Ru₃(CO)₁₂ have been widely studied, and the cluster has been converted to hundreds of derivatives. High pressures of CO convert the cluster to the monomeric ruthenium pentacarbonyl, which reverts to the parent cluster upon standing.
:Ru₃(CO)₁₂ + 3 CO 3 Ru(CO)₅ K_eq = 3.3 x 10⁻⁷ mol dm⁻³ at room temperature
The instability of Ru(CO)₅ contrasts with the robustness of the corresponding Fe(CO)₅. The condensation of Ru(CO)₅ into Ru₃(CO)₁₂ proceeds via initial, rate-limiting loss of CO to give the unstable, coordinatively unsaturated species Ru(CO)₄. This tetracarbonyl binds Ru(CO)₅, initiating the condensation.

Upon warming under a pressure of hydrogen, Ru₃(CO)₁₂ converts to the tetrahedral cluster H₄Ru₄(CO)₁₂. Ru₃(CO)₁₂ undergoes substitution reactions with Lewis bases:
:Ru₃(CO)₁₂ + ''n'' L → Ru₃(CO)_12-''n''L_''n'' + ''n'' CO (''n'' = 1, 2, or 3)
where L is a tertiary phosphine or an isocyanide. It forms complexes with acenaphthylene.

forms a variety of alkene complexes, some where the Ru3 core remains intact but often with fragmentation. Upon treatment with 1,5-cyclooctadiene gives the monoRu tricarbonyl derivative:
:
Upon irradiation with UV light, Ru₃(CO)₁₂ converts to an insoluble polymeric form.

Ru-carbido clusters

At high temperatures, Ru₃(CO)₁₂ converts to a series of clusters that contain interstitial carbido ligands. These include Ru₆C(CO)₁₇ and Ru₅C(CO)₁₅. Anionic carbido clusters are also known, including u₅C(CO)₁₄sup>2− and the bioctahedral cluster u₁₀C₂(CO)₂₄sup>2−.Nicholls, J. N.; Vargas, M. D. "Carbido-Carbonyl Ruthenium Cluster Complexes" Inorganic Syntheses, 1989, volume 26, pages 280-85. Ru₃(CO)₁₂ -derived carbido compounds have been used to synthesize nanoparticles for catalysis. These particles consist of 6-7 atoms and thus are all surface, resulting in extraordinary activity.

References

{{Carbonyl complexes

Organoruthenium compounds
Carbonyl complexes
Chemical compounds containing metal–metal bonds
Ruthenium(0) compounds