Formation of imidates, amides, amines, carbamates, and ureas from the .mu.3-NPh ligands of Fe3(.mu.3-NPh)2(CO)9

The bis(nitrene) cluster Fe3( 3-NPh)2(CO)9 (1) reacts with Li(HBEt3), MeLi, PhLi, and NaOMe to form the formyl and acyl clusters (Fe3( 3-NPh)2(CO)8C)O)R) (4, R = H; 6, R = Ph; 7, R = Me; 8, R = OMe). Formyl cluster 4 is unstable at room temperature and slowly loses CO to form the hydride cluster (HFe3( 3-NPh)2(CO)8) . The benzoyl cluster 7 reacts with EtOTf to yield the nitrene-carbene cluster Fe3( 3-NPh)2(CO)8(C)OEt)Ph)(9) which has been structurally characterized. The carbene and nitrene ligands in 9 couple to form the imidate PhN double bond C(OEt)Ph when 9 is exposed to air or allowed to stand in solution for prolonged periods under CO or N2 atmospheres. Similar nitrene-benzoyl coupling from 7 gives benzanilide, and the methoxycarbonyl and nitrene ligands in 8 couple to give methyl N-phenylcarbamate when the clusters are oxidatively degraded with (FeCp2) . The bis(phosphinidene) cluster Fe3( 3-PPh)2(CO)9 (2) also reacts with PhLi to yield a benzoyl derivative, (Fe3( 3-PPh)2(CO)8(C)O)Ph)) . However, addition of EtOTf to this species does not result in a carbene cluster analogous to 9, but instead phosphinidene-carbene coupling occurs to give Fe3( 2-PPh)( 3-PhPC)OEt)Ph)(CO)9 which has been structurally characterized. The phosphorus atom of the 3-PhPC)OEt)Ph ligand bridgesmore » two iron atoms, and the ethoxy-substituted carbon is attached to the third iron atom.« less