Thermolysis of Ru3(CO)10(dppb): Activation of CH and PPh bonds in PPh2P(CH2)4PPh2 (dppb = 1,4-bis(diphenylphosphino)butane)

The thermolysis reaction of Ru3(CO)10(dppb) 1 for 4 h in refluxing toluene resulted in the formation of Ru3(CO)7(μ3-C6H4)(μ-PPh2){μ-PPhBun} 2, Ru5(CO)14(μ4-PPh){PPh2Bun} 3, Ru3(CO)8(μ3-PPh2CH2CH2CCHPPh2)(μ-H) 4 and Ru3(CO)8(μ3-P(Ph)CHCHCH2CH2PPh2)(μ-H) 5. The transformations involved oxidative addition of aromatic CH and PC bonds to the cluster, elimination of benzene, formation of metal hydride and cluster disproportionation. The molecular structures of complexes 1–5 have been determined by single-crystal X-ray diffraction analysis.

Graphical abstractThe thermolysis reaction of Ru3(CO)10(dppb) 1 for 4 h in refluxing toluene resulted in the formation of Ru3(CO)7(μ3-C6H4)(μ-PPh2){μ-PPhBun} 2, Ru5(CO)14(μ4-PPh){PPh2Bun} 3, Ru3(CO)8(μ3-PPh2CH2CH2CCHPPh2)(μ-H) 4 and Ru3(CO)8(μ3-P(Ph)CHCHCH2CH2PPh2)(μ-H) 5. The transformation of dppb ligand in 1 gives new cluster complexes containing bridging diphenylphosphido, phenylphosphinidene and trapping of benzyne on the trinuclear cluster.Figure optionsDownload full-size imageDownload as PowerPoint slide