The reaction of PP(NO2) with M4(CO)12 (M = Co, Rh) gives the nitrido clusters [M6N(CO)15]- in 13 and 21% yields, respectively. A high yield synthesis (77%) of [Rh6N(CO)15)]- directly from Rh6(CO)16 and PPN(NO2) is also presented. PPN(NO2) reacts with Ir4(CO)12 to give the new isocyanato cluster, [Ir4(NCO)(CO)11]- in 34% yield, while the direct synthesis of this isocyanate product occurs in 77% yield from PPN(N3) and Ir4(CO)12. Modifications of published procedures for the preparation of [N(C2H5)4]2 [Ir6(CO)15] and Ir6(CO)16 are reported that allow shorter reaction times and give higher yields. The reaction of Ir6(CO)16 with one equivalent of PPN(NO2) generates a new cluster, PPN[Ir6(CO)15(NO)], in 57% yield which is proposed to contain a bent nitrosyl ligand. An additional equivalent of PPN(NO2) gives (PPN)2[Ir6(CO)15] in 84% yield with the evolution of N2O as well as CO2.