7-Phosphanorbornene sulfides were used as [RP = S] precursors. The reaction of these precursors with [M(PPh3)4] (M = Pd, Pt) yields star-like M4 clusters in which the central core is coated by three RP = S units acting as 4-electron μ2-P, η2-P = S ligands. The Pd cluster displays both stability and catalytic activity in the Suzuki-Miyaura reaction. DFT analysis suggests that a mononuclear [η2-RP = S]Pd(PPh3) complex is involved in the formation of the Pd4 clusters.