Bimetallic Cluster Complexes: The Synthesis, Structures, and Bonding of Ruthenium Carbonyl Cluster Complexes Containing Palladium and Platinum with the Bulky Tri-tert-butyl-phosphine Ligand

Richard D. Adams, Burjor Captain, Wei Fu, Michael B. Hall, Josiah Manson, Mark D. Smith, Charles Edwin Webster

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Abstract

The bis-phosphine compounds M(PBut3)2, M = Pd and Pt, readily eliminate one PBut3 ligand and transfer MPBut3 groups to the ruthenium-ruthenium bonds in the compounds Ru3(CO)12, Ru6(CO) 176-C), and Ru6(CO)146-C6H6)(μ6-C) without displacement of any of the ligands on the ruthenium complexes. The new compounds, Ru3(CO)12[Pd(PBut3)] 3, 10, and Ru6(CO)176-C)[Pd(PBut3)]2, 11, Ru 6(CO)176-C)[Pt(PBut 3)]n, n = 1 (12), n = 2 (13), and Ru6(CO) 146-C6H6)(μ 6-C)[Pd(PBut3)]n, n = 1 (15), n = 2 (16), have been prepared and structurally characterized. In most cases the MPBut3 groups bridge a pair of mutually bonded ruthenium atoms, and the associated Ru-Ru bond distance increases in length. Fenske-Hall calculations were performed on 10 and 11 to develop an understanding of the electron deficient metal-metal bonding. 10 undergoes a Jahn-Teller distortion to increase bonding interactions between neighboring Ru(CO)4 and Pd(PBut3) fragments. 11 has seven molecular orbitals important to cluster bonding in accord with cluster electron-counting rules.

Original languageEnglish
Pages (from-to)5253-5267
Number of pages15
JournalJournal of the American Chemical Society
Volume126
Issue number16
DOIs
StatePublished - Apr 28 2004
Externally publishedYes

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phosphine
Ruthenium
Palladium
Platinum
Ligands
Metals
Electrons
Jahn-Teller effect
Molecular orbitals
Atoms

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Bimetallic Cluster Complexes : The Synthesis, Structures, and Bonding of Ruthenium Carbonyl Cluster Complexes Containing Palladium and Platinum with the Bulky Tri-tert-butyl-phosphine Ligand. / Adams, Richard D.; Captain, Burjor; Fu, Wei; Hall, Michael B.; Manson, Josiah; Smith, Mark D.; Webster, Charles Edwin.

In: Journal of the American Chemical Society, Vol. 126, No. 16, 28.04.2004, p. 5253-5267.

Research output: Contribution to journalArticle

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abstract = "The bis-phosphine compounds M(PBut3)2, M = Pd and Pt, readily eliminate one PBut3 ligand and transfer MPBut3 groups to the ruthenium-ruthenium bonds in the compounds Ru3(CO)12, Ru6(CO) 17(μ6-C), and Ru6(CO)14(η 6-C6H6)(μ6-C) without displacement of any of the ligands on the ruthenium complexes. The new compounds, Ru3(CO)12[Pd(PBut3)] 3, 10, and Ru6(CO)17(μ 6-C)[Pd(PBut3)]2, 11, Ru 6(CO)17(μ6-C)[Pt(PBut 3)]n, n = 1 (12), n = 2 (13), and Ru6(CO) 14(η6-C6H6)(μ 6-C)[Pd(PBut3)]n, n = 1 (15), n = 2 (16), have been prepared and structurally characterized. In most cases the MPBut3 groups bridge a pair of mutually bonded ruthenium atoms, and the associated Ru-Ru bond distance increases in length. Fenske-Hall calculations were performed on 10 and 11 to develop an understanding of the electron deficient metal-metal bonding. 10 undergoes a Jahn-Teller distortion to increase bonding interactions between neighboring Ru(CO)4 and Pd(PBut3) fragments. 11 has seven molecular orbitals important to cluster bonding in accord with cluster electron-counting rules.",
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N2 - The bis-phosphine compounds M(PBut3)2, M = Pd and Pt, readily eliminate one PBut3 ligand and transfer MPBut3 groups to the ruthenium-ruthenium bonds in the compounds Ru3(CO)12, Ru6(CO) 17(μ6-C), and Ru6(CO)14(η 6-C6H6)(μ6-C) without displacement of any of the ligands on the ruthenium complexes. The new compounds, Ru3(CO)12[Pd(PBut3)] 3, 10, and Ru6(CO)17(μ 6-C)[Pd(PBut3)]2, 11, Ru 6(CO)17(μ6-C)[Pt(PBut 3)]n, n = 1 (12), n = 2 (13), and Ru6(CO) 14(η6-C6H6)(μ 6-C)[Pd(PBut3)]n, n = 1 (15), n = 2 (16), have been prepared and structurally characterized. In most cases the MPBut3 groups bridge a pair of mutually bonded ruthenium atoms, and the associated Ru-Ru bond distance increases in length. Fenske-Hall calculations were performed on 10 and 11 to develop an understanding of the electron deficient metal-metal bonding. 10 undergoes a Jahn-Teller distortion to increase bonding interactions between neighboring Ru(CO)4 and Pd(PBut3) fragments. 11 has seven molecular orbitals important to cluster bonding in accord with cluster electron-counting rules.

AB - The bis-phosphine compounds M(PBut3)2, M = Pd and Pt, readily eliminate one PBut3 ligand and transfer MPBut3 groups to the ruthenium-ruthenium bonds in the compounds Ru3(CO)12, Ru6(CO) 17(μ6-C), and Ru6(CO)14(η 6-C6H6)(μ6-C) without displacement of any of the ligands on the ruthenium complexes. The new compounds, Ru3(CO)12[Pd(PBut3)] 3, 10, and Ru6(CO)17(μ 6-C)[Pd(PBut3)]2, 11, Ru 6(CO)17(μ6-C)[Pt(PBut 3)]n, n = 1 (12), n = 2 (13), and Ru6(CO) 14(η6-C6H6)(μ 6-C)[Pd(PBut3)]n, n = 1 (15), n = 2 (16), have been prepared and structurally characterized. In most cases the MPBut3 groups bridge a pair of mutually bonded ruthenium atoms, and the associated Ru-Ru bond distance increases in length. Fenske-Hall calculations were performed on 10 and 11 to develop an understanding of the electron deficient metal-metal bonding. 10 undergoes a Jahn-Teller distortion to increase bonding interactions between neighboring Ru(CO)4 and Pd(PBut3) fragments. 11 has seven molecular orbitals important to cluster bonding in accord with cluster electron-counting rules.

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