Addition of Pt(PBut3) groups to Ru 5(CO)126-C6H 6)(μ5-C). Synthesis, structures, and dynamical activity

Richard D. Adams, Burjor Captain, Perry J. Pellechia, Lei Zhu

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Abstract

The reaction of Ru5(CO)126-C 6H6)(μ5-C), 7, with Pt(PBut 3)2 yielded two products Ru5(CO) 126-C6H6)(μ6-C) [Pt(PBut3)], 8, and Ru5(CO)126-C6H6)(μ6-C)[Pt(PBu t3)]2, 9. Compound 8 contains a Ru 5Pt metal core in an open octahedral structure. In solution, 8 exists as a mixture of two isomers that interconvert rapidly on the NMR time scale at 20 °C, ΔH‡ = 7.1(1) kcal mol-1, ΔS‡ = -5.1(6) cal mol-1 K-1, and ΔG298‡ = 8.6(3) kcal mol-1. Compound 9 is structurally similar to 8, but has an additional Pt(PBut3) group bridging an Ru-Ru edge of the cluster. The two Pt(PBut3) groups in 9 rapidly exchange on the NMR time scale at 70 °C, ΔH‡ = 9.2(3) kcal mol-1, ΔS‡ = -5(1) cal mol-1 K-1, and ΔG298‡ = 10.7(7) kcal mol-1. Compound 8 reacts with hydrogen to give the dihydrido complex Ru5(CO) 116-C6H6)(μ6-C) [Pt(PBut3)](μ-H)2, 10, in 59% yield. This compound consists of a closed Ru5Pt octahedron with two hydride ligands bridging two of the four Pt-Ru bonds.

Original languageEnglish
Pages (from-to)7243-7249
Number of pages7
JournalInorganic Chemistry
Volume43
Issue number22
DOIs
StatePublished - Nov 1 2004
Externally publishedYes

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Carbon Monoxide
nuclear magnetic resonance
synthesis
hydrides
isomers
Nuclear magnetic resonance
ligands
hydrogen
products
Hydrides
Isomers
metals
Hydrogen
Metals
Ligands

ASJC Scopus subject areas

  • Inorganic Chemistry

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Addition of Pt(PBut3) groups to Ru 5(CO)126-C6H 6)(μ5-C). Synthesis, structures, and dynamical activity. / Adams, Richard D.; Captain, Burjor; Pellechia, Perry J.; Zhu, Lei.

In: Inorganic Chemistry, Vol. 43, No. 22, 01.11.2004, p. 7243-7249.

Research output: Contribution to journalArticle

Adams, Richard D. ; Captain, Burjor ; Pellechia, Perry J. ; Zhu, Lei. / Addition of Pt(PBut3) groups to Ru 5(CO)126-C6H 6)(μ5-C). Synthesis, structures, and dynamical activity. In: Inorganic Chemistry. 2004 ; Vol. 43, No. 22. pp. 7243-7249.
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title = "Addition of Pt(PBut3) groups to Ru 5(CO)12(η6-C6H 6)(μ5-C). Synthesis, structures, and dynamical activity",
abstract = "The reaction of Ru5(CO)12(η6-C 6H6)(μ5-C), 7, with Pt(PBut 3)2 yielded two products Ru5(CO) 12(η6-C6H6)(μ6-C) [Pt(PBut3)], 8, and Ru5(CO)12(η 6-C6H6)(μ6-C)[Pt(PBu t3)]2, 9. Compound 8 contains a Ru 5Pt metal core in an open octahedral structure. In solution, 8 exists as a mixture of two isomers that interconvert rapidly on the NMR time scale at 20 °C, ΔH‡ = 7.1(1) kcal mol-1, ΔS‡ = -5.1(6) cal mol-1 K-1, and ΔG298‡ = 8.6(3) kcal mol-1. Compound 9 is structurally similar to 8, but has an additional Pt(PBut3) group bridging an Ru-Ru edge of the cluster. The two Pt(PBut3) groups in 9 rapidly exchange on the NMR time scale at 70 °C, ΔH‡ = 9.2(3) kcal mol-1, ΔS‡ = -5(1) cal mol-1 K-1, and ΔG298‡ = 10.7(7) kcal mol-1. Compound 8 reacts with hydrogen to give the dihydrido complex Ru5(CO) 11(η6-C6H6)(μ6-C) [Pt(PBut3)](μ-H)2, 10, in 59{\%} yield. This compound consists of a closed Ru5Pt octahedron with two hydride ligands bridging two of the four Pt-Ru bonds.",
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N2 - The reaction of Ru5(CO)12(η6-C 6H6)(μ5-C), 7, with Pt(PBut 3)2 yielded two products Ru5(CO) 12(η6-C6H6)(μ6-C) [Pt(PBut3)], 8, and Ru5(CO)12(η 6-C6H6)(μ6-C)[Pt(PBu t3)]2, 9. Compound 8 contains a Ru 5Pt metal core in an open octahedral structure. In solution, 8 exists as a mixture of two isomers that interconvert rapidly on the NMR time scale at 20 °C, ΔH‡ = 7.1(1) kcal mol-1, ΔS‡ = -5.1(6) cal mol-1 K-1, and ΔG298‡ = 8.6(3) kcal mol-1. Compound 9 is structurally similar to 8, but has an additional Pt(PBut3) group bridging an Ru-Ru edge of the cluster. The two Pt(PBut3) groups in 9 rapidly exchange on the NMR time scale at 70 °C, ΔH‡ = 9.2(3) kcal mol-1, ΔS‡ = -5(1) cal mol-1 K-1, and ΔG298‡ = 10.7(7) kcal mol-1. Compound 8 reacts with hydrogen to give the dihydrido complex Ru5(CO) 11(η6-C6H6)(μ6-C) [Pt(PBut3)](μ-H)2, 10, in 59% yield. This compound consists of a closed Ru5Pt octahedron with two hydride ligands bridging two of the four Pt-Ru bonds.

AB - The reaction of Ru5(CO)12(η6-C 6H6)(μ5-C), 7, with Pt(PBut 3)2 yielded two products Ru5(CO) 12(η6-C6H6)(μ6-C) [Pt(PBut3)], 8, and Ru5(CO)12(η 6-C6H6)(μ6-C)[Pt(PBu t3)]2, 9. Compound 8 contains a Ru 5Pt metal core in an open octahedral structure. In solution, 8 exists as a mixture of two isomers that interconvert rapidly on the NMR time scale at 20 °C, ΔH‡ = 7.1(1) kcal mol-1, ΔS‡ = -5.1(6) cal mol-1 K-1, and ΔG298‡ = 8.6(3) kcal mol-1. Compound 9 is structurally similar to 8, but has an additional Pt(PBut3) group bridging an Ru-Ru edge of the cluster. The two Pt(PBut3) groups in 9 rapidly exchange on the NMR time scale at 70 °C, ΔH‡ = 9.2(3) kcal mol-1, ΔS‡ = -5(1) cal mol-1 K-1, and ΔG298‡ = 10.7(7) kcal mol-1. Compound 8 reacts with hydrogen to give the dihydrido complex Ru5(CO) 11(η6-C6H6)(μ6-C) [Pt(PBut3)](μ-H)2, 10, in 59% yield. This compound consists of a closed Ru5Pt octahedron with two hydride ligands bridging two of the four Pt-Ru bonds.

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