ADDUCTS OF TRIGONAL-PRISMATIC AND OCTAHEDRAL METAL-CLUSTERS CONTAINING INTERSTITIAL ATOMS (NITROGEN OR CARBON) WITH [AU(PPH(3))](+)

Spectroscopic evidence indicates that the anion [Rh6N(CO)(15)](-) reac ts with [Au(PPh(3))Cl] to afford [Rh6N(CO)(15){Au(PPh(3))}], but there is no evidence that a similar reaction with either CF3CO2H or HBF4 . Et(2)O leads to [Rh-6(H)N(CO)(15)]. Addition of [Au(PPh(3))Cl] to [Rh6 C(CO)(13)](2-) at -80 degrees C gives [Rh6C(CO)(13){Au(PPh(3))}](-), i n which there is complete migration of the Au(PPh(3)) group and all th e carbonyls around the Rh-6 octahedron even at -80 degrees C. At highe r temperatures, [Rh6C(CO)(13){Au(PPh(3))}](-) loses CO and forms [Rh6C (CO)(12){Au(PPh(3))}](-), which has been characterised by a variety of multinuclear NMR measurements. Spectroscopic evidence is presented to suggest that a related 84-electron octahedral cluster [Rh6N(CO)(12)]( -) is formed, rather than the 86-electron cluster [Rh6N(CO)(13)](-), o n heating [Rh6N(CO)(15)](-).