Abstract: Seven new metal-metal singly bonded compounds of the unsymmetrical type η⁵>-R¹>C₅H₄(CO)₃Mo-Mo(CO)₃C₅H₄R²>-η⁵>(R¹>, R²>:C(O)Me, CO₂Et), η⁵>-R¹>C₅H₄(CO)₃W-W(CO)₃C₅H₄R²>-η⁵>-(R¹>, R²>:C(O)Me, CO₂Et;H, CO₂Et) andη⁵>-R¹> C₅H₄(CO)₃Mo-W(CO)₃C₅H₄R²>-η⁵>(R¹>, R²>:C(O)Me, H; Et, C(O)Me; C(O)Me, n-Bu; CO₂Me, n-Bu)have been successfully synthesized by oxidative coupling reaction between η⁵>-R¹>C₅H₄(CO₂)₂MNa and η⁵>-R²>C₅H₄(CO)₃MNa(M=Mo, W) and between η⁵>-R¹> C₅H₄(CO)₃MoNa and η⁵>-R²>C₅H₄(CO)₃WNa in the presence of Fe₂(SO₄)₃/HOAc/H₂O reagents. The structures of 1-7 were well characterized by C/Hanalysis, MS, IRand ¹H NMRspectroscopy, and the features of this kind of reaction were discussed briefly.

Key words: Oxidative cross-coupling, Oxidative homo-coupling, Metal-metal bonded compound, Organomolybdenum, Organotungsten