CHEMISTRY OF THE CARBIDO-DECARUTHENIUM AND NITRIDO-DECARUTHENIUM CLUSTER ANIONS [RU10H(C)(CO)(24)](-), [RU10C(CO)(24)](2-) AND [RU10N(CO)(24)](-)

The thermolysis of [RU(3)(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(PPh(3))(2)](+) salt. Deprotonation of 2 yielded the dianion [Ru10C(CO)(24)](2-) 3 which has been similarly characterised. The isostructural decaruthenium nitrido anion [RU(10)N(CO)(24)](-) 4 may be synthesised by condensation of the required stoichiometric quantities of [RU(3)(CO)(12)] with the preformed nitrides [RU(5)N(CO)(14)](-) or [Ru6N(CO)(16)](-) under thermolysis in bis(2-methoxyethyl) ether (diglyme), or alternatively directly from [Ru-3(CO)(12)] by reaction with 1/3 equivalent of [N(PPh(3))(2)][N-3] under the-same conditions. The anion 4 as its [N(PPh(3))(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 N-14 NMR resonance at delta 30 [delta(N-14, MeNO(2)) = 0]. Reaction of 3 with 1 atm CO in solution leads to rapid degradation to [Ru6C(CO)(16)](2)- and [Ru-3(CO)(12)]whilst under the same conditions 4 yields [Ru5N(CO)(14)](-) and [RU(3)(CO)(12)].