DOUBLE DEOXYGENATION OF PPN(NO2) USING METAL CARBONYL CLUSTERS OF COBALT, RHODIUM, AND IRIDIUM

Article abstract of DOI:10.1016/0022-328X(85)80076-0

The reaction of PPN(NO2) with M4(CO)12 (M = Co, Rh) gives the nitrido clusters ^- in 13 and 21percent yields, respectively.A high yield synthesis (77percent) of ^- directly from Rh(CO)16 and PPN(NO2) is also presented.PPN(NO2) reacts with Ir4(CO)12 to give the new isocyanato cluster, ^- in 34percent yield, while the direct synthesis of this isocyanate product occurs in 77percent yield from PPN(N3) and Ir(CO)12.Modifications of published procedures for the preparation of 2 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, in 57percent yield which is proposed to contain a bent nitrosyl ligand.An additional equivalent of PPN(NO2) gives (PPN)2 in 84percent yield with the evolution of N2O as well as CO2.