Platinum-Rhodium Carbonyl Clusters

New Structures and New Types of Dynamical Activity

Richard D. Adams, Burjor Captain, Perry J. Pellechia, Jack L. Smith

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

The reaction of Rh4(CO)12 with Pt(PBu t3)2 in CH2Cl2 at room temperature yielded three new complexes: Rh4(CO)4-(μ -CO)44-CO)(PBut3) 2[Pt(PBut3)], 10, Rh2(CO) 8[Pt(PBut3)]2[Pt(CO)], 11, and Rh 2(CO)8[Pt(PBut3)]3, 12. The reaction of Rh4(CO)12 with an excess of Pt(PBu t3)2 in hexane at 68 °C yielded the new hexarhodium-tetraplatinum compound, Rh6(CO)16[Pt(PBu t3)]4, 13, in a low yield. All four compounds were characterized by 31P NMR and single-crystal X-ray diffraction analyses. Compound 10 contains an unsymmetrical quadruply bridging carbonyl ligand in the fold of a butterfly tetrahedral cluster of four rhodium atoms with a Pt(PBut3) group bridging the hinge of the butterfly tetrahedron. Compound 11 contains an unsaturated trigonal bipyramidal Rh2Pt3 cluster. Compound 12 is similar to 11 except the trigonal bipyramidal Rh2Pt3 cluster opened by cleavage of one Pt-Rh bond due to steric interactions produced by the replacement of one of the carbonyl ligands in 11 with a tri-tert-butylphosphine ligand. Compound 12 undergoes facile dynamical rearrangements of the metal atoms in the cluster which average the three inequivalent phosphine ligands on the platinum atoms. Compound 13 contains an octahedral cluster of six rhodium atoms with four Pt(PBut3) groups bridging edges of that octahedron.

Original languageEnglish
Pages (from-to)2695-2702
Number of pages8
JournalInorganic Chemistry
Volume43
Issue number8
DOIs
StatePublished - Apr 19 2004
Externally publishedYes

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Rhodium
Platinum
rhodium
platinum
Ligands
Atoms
phosphine
ligands
atoms
Hexanes
Hinges
complex compounds
hinges
phosphines
tetrahedrons
Metals
Nuclear magnetic resonance
Single crystals
cleavage
X ray diffraction

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Platinum-Rhodium Carbonyl Clusters : New Structures and New Types of Dynamical Activity. / Adams, Richard D.; Captain, Burjor; Pellechia, Perry J.; Smith, Jack L.

In: Inorganic Chemistry, Vol. 43, No. 8, 19.04.2004, p. 2695-2702.

Research output: Contribution to journalArticle

Adams, Richard D. ; Captain, Burjor ; Pellechia, Perry J. ; Smith, Jack L. / Platinum-Rhodium Carbonyl Clusters : New Structures and New Types of Dynamical Activity. In: Inorganic Chemistry. 2004 ; Vol. 43, No. 8. pp. 2695-2702.
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abstract = "The reaction of Rh4(CO)12 with Pt(PBu t3)2 in CH2Cl2 at room temperature yielded three new complexes: Rh4(CO)4-(μ -CO)4(μ4-CO)(PBut3) 2[Pt(PBut3)], 10, Rh2(CO) 8[Pt(PBut3)]2[Pt(CO)], 11, and Rh 2(CO)8[Pt(PBut3)]3, 12. The reaction of Rh4(CO)12 with an excess of Pt(PBu t3)2 in hexane at 68 °C yielded the new hexarhodium-tetraplatinum compound, Rh6(CO)16[Pt(PBu t3)]4, 13, in a low yield. All four compounds were characterized by 31P NMR and single-crystal X-ray diffraction analyses. Compound 10 contains an unsymmetrical quadruply bridging carbonyl ligand in the fold of a butterfly tetrahedral cluster of four rhodium atoms with a Pt(PBut3) group bridging the hinge of the butterfly tetrahedron. Compound 11 contains an unsaturated trigonal bipyramidal Rh2Pt3 cluster. Compound 12 is similar to 11 except the trigonal bipyramidal Rh2Pt3 cluster opened by cleavage of one Pt-Rh bond due to steric interactions produced by the replacement of one of the carbonyl ligands in 11 with a tri-tert-butylphosphine ligand. Compound 12 undergoes facile dynamical rearrangements of the metal atoms in the cluster which average the three inequivalent phosphine ligands on the platinum atoms. Compound 13 contains an octahedral cluster of six rhodium atoms with four Pt(PBut3) groups bridging edges of that octahedron.",
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AB - The reaction of Rh4(CO)12 with Pt(PBu t3)2 in CH2Cl2 at room temperature yielded three new complexes: Rh4(CO)4-(μ -CO)4(μ4-CO)(PBut3) 2[Pt(PBut3)], 10, Rh2(CO) 8[Pt(PBut3)]2[Pt(CO)], 11, and Rh 2(CO)8[Pt(PBut3)]3, 12. The reaction of Rh4(CO)12 with an excess of Pt(PBu t3)2 in hexane at 68 °C yielded the new hexarhodium-tetraplatinum compound, Rh6(CO)16[Pt(PBu t3)]4, 13, in a low yield. All four compounds were characterized by 31P NMR and single-crystal X-ray diffraction analyses. Compound 10 contains an unsymmetrical quadruply bridging carbonyl ligand in the fold of a butterfly tetrahedral cluster of four rhodium atoms with a Pt(PBut3) group bridging the hinge of the butterfly tetrahedron. Compound 11 contains an unsaturated trigonal bipyramidal Rh2Pt3 cluster. Compound 12 is similar to 11 except the trigonal bipyramidal Rh2Pt3 cluster opened by cleavage of one Pt-Rh bond due to steric interactions produced by the replacement of one of the carbonyl ligands in 11 with a tri-tert-butylphosphine ligand. Compound 12 undergoes facile dynamical rearrangements of the metal atoms in the cluster which average the three inequivalent phosphine ligands on the platinum atoms. Compound 13 contains an octahedral cluster of six rhodium atoms with four Pt(PBut3) groups bridging edges of that octahedron.

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