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| - High Nuclearity Iridium−Platinum Clusters: Synthesis,Structures, Bonding, and Reactivity
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| - The reaction of Ir4(CO)12 with an excess of Pt(PBut3)2 at room temperature yielded the bis-Pt(PBut3) adduct Ir4(CO)12[Pt(PBut3)]2 (9), which contains two Pt(PBut3) groups bridging opposite edges ofa central Ir4 pseudotetrahedron. The same reaction at 110 °C yielded two new higher nuclearity complexes,Ir8(CO)12[Pt(PBut3)]4 (10) and Ir6(CO)10[Pt(PBut3)]4 (11). Compound 10 consists of a central Ir4(CO)4tetrahedron with four edge-bridging Ir(CO)2 groups and four Pt(PBut3) groups that are each bonded to Ir3triangles of the Ir4 tetrahedron and two of the Ir(CO)2 groups. Compound 11 consists of a central Ir4(CO)4pseudotetrahedron with two edge-bridging Ir(CO)2 groups and four Pt(PBut3) groups; one Pt(PBut3) groupis bonded to five iridium atoms as found in 10; two are bonded to four iridium atoms, and one is bondedto one of the outer Ir2Pt triangles. Compound 11 reacted with hydrogen at 97 °C to give the new tetrahydridocomplex Ir6(CO)8[Pt(PBut3)]4(μ-H)4 (12). Compound 12 is formed by the loss of the two bridging carbonylligands from 11 and the addition of four hydrido ligands. All four new compounds were characterized byboth 1H and 31P NMR and by single-crystal X-ray diffraction analyses. The bonding in 9 was studied byFenske−Hall molecular orbital calculations, which in this case provides a delocalized bonding descriptionfor the Ir−Ir and Ir−Pt bonding, where the attachment of the 0 e- fragments of Pt(PR3) use Ir−Ir bondingorbitals of the Ir4(CO)12 cluster to form multicenter Pt−Ir bonds.
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