Chemistry of the carbido- and nitrido-decaruthenium cluster anions [Ru10H(C)(CO)24]–, [Ru10C(CO)24]2– and [Ru10N(CO)24]–

Abstract

The thermolysis of [Ru₃(CO)₁₂]1 in the presence of 1,3,5-trimethylbenzene yielded, in addition to hexaruthenium carbido products, the tetracapped octahedral carbido cluster anion [Ru₁₀H(C)(CO)₂₄]^–2 which has been fully characterised as its [N(PPh₃)₂]⁺ salt. Deprotonation of 2 yielded the dianion [Ru₁₀C(CO)₂₄]^2–3 which has been similarly characterised. The isostructural decaruthenium nitrido anion [Ru₁₀N(CO)₂₄]^–4 may be synthesised by condensation of the required stoichiometric quantities of [Ru₃(CO)₁₂] with the preformed nitrides [Ru₅N(CO)₁₄]^– or [Ru₆N(CO)₁₆]^– under thermolysis in bis(2-methoxyethyl) ether (diglyme), or alternatively directly from [Ru₃(CO)₁₂] by reaction with 1/3 equivalent of [N(PPh₃)₂][N₃] under the same conditions. The anion 4 as its [N(PPh₃)₂]⁺ salt forms crystals isomorphous to those of 2, and conclusive evidence for its containing an interstitial nitride was therefore obtained by observation of its ¹⁴N NMR resonance at δ 30 [δ(¹⁴N, MeNO₂)= 0]. Reaction of 3 with 1 atm CO in solution leads to rapid degradation to [Ru₆C(CO)₁₆]^2– and [Ru₃(CO)₁₂] whilst under the same conditions 4 yields [Ru₅N(CO)₁₄]^– and [Ru₃(CO)₁₂].