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Cluster synthesis 37—Platinum-ruthenium carbido-cluster complexes: The syntheses and structural characterizations of PtRu5(C)(CO)16, Pt2Ru5(C)(CO)13(COD)2, and Pt3Ru5(C)(CO)14(COD)2

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From the reaction of [Ru5(C)(CO)14]2− with Pt(COD)Cl2, COD=1, 5 cyclooctadiene, the new platinum-ruthenium carbido cluster complex PtRu5 (C)(CO)14(COD),1, was obtained in 41% yield. When1 was allowed to react with carbon monoxide (25°C/1 atm), the new complex PtRu5(C)(CO)16,2, was obtained almost quantitatively (97% yield). Compound2 was characterized by IR and single-crystal X-ray diffraction analysis. The six metal atoms are arranged in the form of an octahedron with the carbide ligand located in the center. Compound1 is believed to have a similar structure to2 except for a COD ligand coordinated to the platinum atom. When activated by treatment with Me3NO, compound2 reacts with Pt(COD)2 at 25°C to yield two higher nuclearity cluster complexes, Pt2Ru5C(CO)13(COD)2.3, and Pt3Ru5C(CO)14(COD)2,4. The structure of3 is similar to that of1, but contains a Pt(COD) grouping capping one Ru3 triangle of the PtRu5 octahedron. The structure of4 consists of a PtRu5 octahedron with two Pt(COD) capping groups, one on an Ru3 triangle and the other on a PtRu2 triangle of the octahedron. Crystal data: for2, space group=P21/n,a=9.341 (2) Å,b=14.957 (3) Å,c=36.80 (1) Å, β=90.38 (2) °,Z=8, 4034 reflections,R=0.030, for3, space group=P21/c,a=14.998 (3) Å,b=10.288 (3) Å,c=26.581 (7) Å, β=102.75 (2) °,Z=4, 2917 reflections,R=0.028. for4, space group=P21/n,a=13.412 (4) Å,b=16.252 (4) Å,c=20.107 (4) Å, β=106.13 (2) °,Z=4, 2745 reflections,R=0.032.

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Correspondence to Richard D. Adams.

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Adams, R.D., Wu, W. Cluster synthesis 37—Platinum-ruthenium carbido-cluster complexes: The syntheses and structural characterizations of PtRu5(C)(CO)16, Pt2Ru5(C)(CO)13(COD)2, and Pt3Ru5(C)(CO)14(COD)2 . J Clust Sci 2, 271–290 (1991). https://doi.org/10.1007/BF00702957

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Key words

  • Interstitial carbido ligands
  • mixed metal clusters
  • dianionic cluster
  • crystallographic structure
  • platinum
  • ruthenium