Facile activation of hydrogen by unsaturated platinum-osmium carbonyl cluster complexes

Richard D. Adams, Burjor Captain, Lei Zhu

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The electronically unsaturated cluster complex Os3Pt2(CO)10(PBut3)2 (10) was obtained from the reaction of Os3(CO)10(NCMe)2 with Pt(PBut3)2. Three side products: PtOs3(CO)10(PBut2)CMe2CH2(μ-H) (13), Os3(CO)10(PBut3)2 (14) and Pt2Os3(CO)10(PBut3)(PBut2)CMe2CH2(μ-H) (15) were also obtained from this reaction. The three osmium atoms in 10 lie in the equatorial plane of a trigonal bipyramid. The platinum atoms occupy the apical positions. When heated, compound 10 was converted to 15 by metallation of one of the methyl groups of one of the PBut3 ligands at the platinum atom to which it is coordinated. The platinum atom then shifted to an edge of the Os3 triangle by cleaving one of its Pt-Os bonds. Compound 13 also contains a metallated PBut3 ligand attached to the platinum atom of the tetrahedral PtOs3 cluster. Compound 10 reacts with hydrogen at 0 °C to yield the di- and tetra-hydrido compounds Os3Pt2(CO)10(PBut3)2(μ-H)2 (11) and Os3Pt2(CO)10(PBut3)2(μ-H)4 (12) with the hydrido ligands bridging Os-Pt and Os-Os bonds. With each addition of hydrogen, one of the platinum atoms in the cluster was shifted to an edge of the Os3triangle. When solutions of 12 at 25 °C were purged with nitrogen, hydrogen was eliminated and the compounds 10 and 11 were regenerated. The electronic structures of 10 and 11 were also investigated by Fenske-Hall molecular orbital theory. When compound 10 was exposed to hydrogen for 2.5 h, compound 12 was formed together with the new tetranuclear metal cluster complexes PtOs3(CO)10(PBut3)(μ-H)2 (16), PtOs3(CO)9(PBut3)(μ-H)4 (17) and PtOs3(CO)8(PBut3)2(μ-H)4 (18). Compounds 16-18 contain tetrahedrally shaped clusters of four metal atoms with bridging hydrido ligands. All new compounds were characterized structurally by single-crystal X-ray diffraction methods.

Original languageEnglish
Pages (from-to)819-833
Number of pages15
JournalJournal of Organometallic Chemistry
Volume693
Issue number5
DOIs
StatePublished - Mar 1 2008
Externally publishedYes

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Osmium
osmium
Platinum
Hydrogen
platinum
Chemical activation
activation
Atoms
Ligands
hydrogen
atoms
ligands
Coordination Complexes
Metals
X-Ray Diffraction
Nitrogen
Molecular orbitals
metal clusters
triangles
Electronic structure

Keywords

  • Bimetallic
  • Bulky ligands
  • Hydrogen activation
  • Osmium
  • Platinum
  • Unsaturation

ASJC Scopus subject areas

  • Chemical Engineering (miscellaneous)
  • Materials Science (miscellaneous)
  • Materials Chemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Biochemistry

Cite this

Facile activation of hydrogen by unsaturated platinum-osmium carbonyl cluster complexes. / Adams, Richard D.; Captain, Burjor; Zhu, Lei.

In: Journal of Organometallic Chemistry, Vol. 693, No. 5, 01.03.2008, p. 819-833.

Research output: Contribution to journalArticle

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title = "Facile activation of hydrogen by unsaturated platinum-osmium carbonyl cluster complexes",
abstract = "The electronically unsaturated cluster complex Os3Pt2(CO)10(PBut3)2 (10) was obtained from the reaction of Os3(CO)10(NCMe)2 with Pt(PBut3)2. Three side products: PtOs3(CO)10(PBut2)CMe2CH2(μ-H) (13), Os3(CO)10(PBut3)2 (14) and Pt2Os3(CO)10(PBut3)(PBut2)CMe2CH2(μ-H) (15) were also obtained from this reaction. The three osmium atoms in 10 lie in the equatorial plane of a trigonal bipyramid. The platinum atoms occupy the apical positions. When heated, compound 10 was converted to 15 by metallation of one of the methyl groups of one of the PBut3 ligands at the platinum atom to which it is coordinated. The platinum atom then shifted to an edge of the Os3 triangle by cleaving one of its Pt-Os bonds. Compound 13 also contains a metallated PBut3 ligand attached to the platinum atom of the tetrahedral PtOs3 cluster. Compound 10 reacts with hydrogen at 0 °C to yield the di- and tetra-hydrido compounds Os3Pt2(CO)10(PBut3)2(μ-H)2 (11) and Os3Pt2(CO)10(PBut3)2(μ-H)4 (12) with the hydrido ligands bridging Os-Pt and Os-Os bonds. With each addition of hydrogen, one of the platinum atoms in the cluster was shifted to an edge of the Os3triangle. When solutions of 12 at 25 °C were purged with nitrogen, hydrogen was eliminated and the compounds 10 and 11 were regenerated. The electronic structures of 10 and 11 were also investigated by Fenske-Hall molecular orbital theory. When compound 10 was exposed to hydrogen for 2.5 h, compound 12 was formed together with the new tetranuclear metal cluster complexes PtOs3(CO)10(PBut3)(μ-H)2 (16), PtOs3(CO)9(PBut3)(μ-H)4 (17) and PtOs3(CO)8(PBut3)2(μ-H)4 (18). Compounds 16-18 contain tetrahedrally shaped clusters of four metal atoms with bridging hydrido ligands. All new compounds were characterized structurally by single-crystal X-ray diffraction methods.",
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AU - Adams, Richard D.

AU - Captain, Burjor

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N2 - The electronically unsaturated cluster complex Os3Pt2(CO)10(PBut3)2 (10) was obtained from the reaction of Os3(CO)10(NCMe)2 with Pt(PBut3)2. Three side products: PtOs3(CO)10(PBut2)CMe2CH2(μ-H) (13), Os3(CO)10(PBut3)2 (14) and Pt2Os3(CO)10(PBut3)(PBut2)CMe2CH2(μ-H) (15) were also obtained from this reaction. The three osmium atoms in 10 lie in the equatorial plane of a trigonal bipyramid. The platinum atoms occupy the apical positions. When heated, compound 10 was converted to 15 by metallation of one of the methyl groups of one of the PBut3 ligands at the platinum atom to which it is coordinated. The platinum atom then shifted to an edge of the Os3 triangle by cleaving one of its Pt-Os bonds. Compound 13 also contains a metallated PBut3 ligand attached to the platinum atom of the tetrahedral PtOs3 cluster. Compound 10 reacts with hydrogen at 0 °C to yield the di- and tetra-hydrido compounds Os3Pt2(CO)10(PBut3)2(μ-H)2 (11) and Os3Pt2(CO)10(PBut3)2(μ-H)4 (12) with the hydrido ligands bridging Os-Pt and Os-Os bonds. With each addition of hydrogen, one of the platinum atoms in the cluster was shifted to an edge of the Os3triangle. When solutions of 12 at 25 °C were purged with nitrogen, hydrogen was eliminated and the compounds 10 and 11 were regenerated. The electronic structures of 10 and 11 were also investigated by Fenske-Hall molecular orbital theory. When compound 10 was exposed to hydrogen for 2.5 h, compound 12 was formed together with the new tetranuclear metal cluster complexes PtOs3(CO)10(PBut3)(μ-H)2 (16), PtOs3(CO)9(PBut3)(μ-H)4 (17) and PtOs3(CO)8(PBut3)2(μ-H)4 (18). Compounds 16-18 contain tetrahedrally shaped clusters of four metal atoms with bridging hydrido ligands. All new compounds were characterized structurally by single-crystal X-ray diffraction methods.

AB - The electronically unsaturated cluster complex Os3Pt2(CO)10(PBut3)2 (10) was obtained from the reaction of Os3(CO)10(NCMe)2 with Pt(PBut3)2. Three side products: PtOs3(CO)10(PBut2)CMe2CH2(μ-H) (13), Os3(CO)10(PBut3)2 (14) and Pt2Os3(CO)10(PBut3)(PBut2)CMe2CH2(μ-H) (15) were also obtained from this reaction. The three osmium atoms in 10 lie in the equatorial plane of a trigonal bipyramid. The platinum atoms occupy the apical positions. When heated, compound 10 was converted to 15 by metallation of one of the methyl groups of one of the PBut3 ligands at the platinum atom to which it is coordinated. The platinum atom then shifted to an edge of the Os3 triangle by cleaving one of its Pt-Os bonds. Compound 13 also contains a metallated PBut3 ligand attached to the platinum atom of the tetrahedral PtOs3 cluster. Compound 10 reacts with hydrogen at 0 °C to yield the di- and tetra-hydrido compounds Os3Pt2(CO)10(PBut3)2(μ-H)2 (11) and Os3Pt2(CO)10(PBut3)2(μ-H)4 (12) with the hydrido ligands bridging Os-Pt and Os-Os bonds. With each addition of hydrogen, one of the platinum atoms in the cluster was shifted to an edge of the Os3triangle. When solutions of 12 at 25 °C were purged with nitrogen, hydrogen was eliminated and the compounds 10 and 11 were regenerated. The electronic structures of 10 and 11 were also investigated by Fenske-Hall molecular orbital theory. When compound 10 was exposed to hydrogen for 2.5 h, compound 12 was formed together with the new tetranuclear metal cluster complexes PtOs3(CO)10(PBut3)(μ-H)2 (16), PtOs3(CO)9(PBut3)(μ-H)4 (17) and PtOs3(CO)8(PBut3)2(μ-H)4 (18). Compounds 16-18 contain tetrahedrally shaped clusters of four metal atoms with bridging hydrido ligands. All new compounds were characterized structurally by single-crystal X-ray diffraction methods.

KW - Bimetallic

KW - Bulky ligands

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KW - Osmium

KW - Platinum

KW - Unsaturation

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