Pyrolysis of Ru3(m-dppm)(CO)9(PPh3): formation of novel Ru4 and Ru3 clusters

Abstract

Heating RU3(μ-dppm)(CO)9(PPh3) (2) for 90 min in refluxing toluene resulted inthe formation of Ru4(μ4-PPh)(μ4-PPh2C6H4CO)(μ-PPh2CH2)(CO)8 (3) and Ru3{μ3-PPh(C6H4)}(μ-PPh2CH2)(μ-PPh2)(μ-CO)(CO)6 (4) as the major products (41%); other complexes identified were Ru3{μ3-PPhCH2PPh(C6H4)}(CO)9 (5) and Ru2(μ-PPhC6H4PPhCH2)(CO)6−n(PPh3)n[n = 1(6), 0(7)]. The transformations involve oxidative addition of aromatic C---H and P---C bonds to the cluster, elimination of benzene and carbonylation of the aryl-Ru bond, as well as cluster disproportionation. X-ray structures of 3, 4 and 6 are presented.