Bimetallic Clusters of Iron with Palladium and Platinum. Synthesis and Structures of Fe<sub>2</sub>(CO)<sub>9</sub>[M(PBu<sup>t</sup><sub>3</sub>)]<sub>2</sub> (M = Pd or Pt) and Fe<sub>2</sub>(CO)<sub>8</sub>[Pt(PBu<sup>t</sup><sub>3</sub>)]<sub>2</sub>(μ-H)<sub>2</sub>
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The reaction of Fe2(CO)9 with Pd(PBut3)2 and Pt(PBut3)2 yielded the Fe−Pd and Fe−Pt cluster complexes Fe2(CO)9[M(PBut3)]2, M = Pd (8) or Pt (9). The structures of 8 and 9 are analogous and consist of nearly planar butterfly clusters of two palladium/platinum atoms in the wing-tip positions and two mutually bonded iron atoms, Fe−Fe = 2.9582(11) Å in 8 and 2.9100 (9) Å in 9. Compound 8 decomposes to form the mononuclear iron compound Fe(CO)4(PBut3) (11) when heated at 68 °C. The reaction of Pt(PBut3)2 with Fe2(CO)9 in the presence of hydrogen at 127 °C yielded the dihydrido complex Fe2(CO)8[Pt(PBut3)]2(μ-H)2 (10). Compound 10 contains a closed Fe2Pt2 tetrahedral cluster with hydrido ligands bridging two of the Fe−Pt bonds. Compounds 8, 9, and 10 were structurally characterized crystallographically.
