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].