High Nuclearity Iridium−Platinum Clusters: Synthesis, Structures, Bonding, and Reactivity

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 of
a 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)4
tetrahedron with four edge-bridging Ir(CO)2 groups and four Pt(PBut3) groups that are each bonded to Ir3
triangles of the Ir4 tetrahedron and two of the Ir(CO)2 groups. Compound 11 consists of a central Ir4(CO)4
pseudotetrahedron with two edge-bridging Ir(CO)2 groups and four Pt(PBut3) groups; one Pt(PBut3) group
is bonded to five iridium atoms as found in 10; two are bonded to four iridium atoms, and one is bonded
to one of the outer Ir2Pt triangles. Compound 11 reacted with hydrogen at 97 °C to give the new tetrahydrido
complex Ir6(CO)8[Pt(PBut3)]4(μ-H)4 (12). Compound 12 is formed by the loss of the two bridging carbonyl
ligands from 11 and the addition of four hydrido ligands. All four new compounds were characterized by
both 1H and 31P NMR and by single-crystal X-ray diffraction analyses. The bonding in 9 was studied by
Fenske−Hall molecular orbital calculations, which in this case provides a delocalized bonding description
for the Ir−Ir and Ir−Pt bonding, where the attachment of the 0 e- fragments of Pt(PR3) use Ir−Ir bonding
orbitals of the Ir4(CO)12 cluster to form multicenter Pt−Ir bonds.