Stepwise synthesis of heteronuclear Pt2M and PdPtM clusters (M = Cr, Mo, W)

Article abstract of DOI:10.1021/om00149a006

The dinuclear complex (μ-C₅H₅)(μ-2-MeC₃H₄)Pt ₂(P-i-Pr₃)₂ (1), which is prepared from (η⁵-C₅H₅)Pt-(η³-2-MeC ₃H₄) and Pt(P-i-Pr₃)₂, reacts with Me₃SiBr to produce the structurally related compound (μ-2-MeC₃H₄)(μ-Br)Pt₂(P-i-Pr ₃)₂ (4). Reaction of 4 with [(C₅H₅)M(CO)₃]Na (M = Mo, W) leads to displacement of the bridging bromide by the tricarbonyl(cyclopentadienyl)metal anion and formation of the trinuclear clusters (C₅H₅)(2-MeC₃H₄)(CO) ₃(P-i-Pr₃)₂Pt₂M (5, 6). The analogous mixed-metal PdPtM complexes 9-11 are similarly prepared, starting from (μ-C₅H₅)(μ-2-MeC₃H ₄)PdPt(P-i-Pr₃)₂ (7) via (μ-2-MeC₃H₄)(μ-Br)-PdPt(P-i-Pr₃) ₂ (8) as the intermediate that subsequently reacts with [(C₅H₅)M(CO)₃]Na (M = Cr, Mo, W) to form (C₅H₅)(2-MeC₃H₄)(CO) ₃(P-i-Pr₃)₂PdPtM (9-11). The IR and ¹H, ¹³C, and ³¹P NMR spectroscopic data of 5, 6, and 9-11 confirm that the new heteronuclear clusters contain a tetrahedral Pt₂MC or PdPtMC framework, the carbon atom of which belongs to a triply bridging CO group.