Synthesis of Platinum-Triruthenium Clusters Using the Zero-Valent Platinum Reagent Pt(nb)3: X-Ray Crystal Structures of Ru3Pt(CO)11(P-iPr3)2, Ru3Pt(μ-H)(μ3-η3-MeCCHCMe)(CO)9(P-iPr3), Ru3Pt(μ3-η2-PhCCPh)(CO)10(P-iPr3), Ru3Pt(μ-H)(μ4-N)(CO)10(P-iPr3) and Ru3Pt(μ-H)(μ4-η2-NO)(CO)10(P-iPr3)

The complexes Pt(nb)3-n(P-iPr3)n (n=1, 2, nb=bicyclo[2.2.1]hept-2-ene), prepared in situ from Pt(nb)3, are useful reagents for addition of Pt(P-iPr3)n fragments to saturated triruthenium clusters. The complexes Ru3Pt(CO)11(P-iPr3)2 (1), Ru3Pt(μ-H)(μ3-η3-MeCCHCMe)(CO)9(P-iPr3) (2), Ru3Pt(μ3-η2-PhCCPh)(CO)10(P-iPr3) (3), Ru3Pt(μ-H)(μ4-N)(CO)10(P-iPr3) (4) and Ru3Pt(μ-H)(μ4-η2-NO)(CO)10(P-iPr3) (5) have been prepared in this fashion. All complexes have been characterized spectroscopically and by single crystal X-ray determinations. Clusters 1–3 all have 60 cluster valence electrons (CVE) but exhibit differing metal skeletal geometries. Cluster 1 exhibits a planar-rhomboidal metal skeleton with 5 metal–metal bonds and with minor disorder in the metal atoms. Cluster 2 has a distorted tetrahedral metal arrangement, while cluster 3 has a butterfly framework (butterfly angle=118.93(2)°). Clusters 4 and 5 posseses 62 CVE and spiked triangular metal frameworks. Cluster 4 contains a μ4-nitrido ligand, while cluster 5 has a highly unusual μ4-η2-nitrosyl ligand with a very long nitrosyl N–O distance of 1.366(5) Å.