Experimental measure of metal-alkynyl electronic structure interactions by photoelectron spectroscopy: (η5-C5H5)Ru(CO)2CCMe and [(η5-C5H5)Ru(CO)2]2(μ-CC)

Ashley R. Head, Sharon K. Renshaw, Andrew B. Uplinger, Jeffrey R. Lomprey, John P. Selegue, Dennis L. Lichtenberger

Research output: Research - peer-reviewArticle

Abstract

The gas-phase He I and He II photoelectron spectra of the propynylruthenium molecule CpRu(CO)2CCMe (Cp = η5-C5H5) and the ethynediyldiruthenium molecule [CpRu(CO)2]2(μ-CC) are compared with the spectrum of CpRu(CO)2Cl to experimentally determine electronic structure interactions of the alkynyl ligands with the metal. The spectra indicate that the interaction between the filled metal-dπ and filled alkynyl-π orbitals dominates the metal-alkynyl π electronic structure, mirroring previously characterized CpFe(CO)2 alkynyls. All valence ionizations of the Ru molecules are stabilized with respect to similar Fe compounds, contrary to the common expectation of lower ionization energies with atomic substitution down a column of the periodic table. Ab initio electronic structure calculations suggest that this stabilization traces to the greater inherent electronic relaxation energy associated with removal of Fe 3d electrons compared to removal of Ru 4d electrons. Destabilization of the first two ionization bands of the diruthenium molecule are a result of filled-filled interactions between alkynyl π-bonds with the symmetric combination of metal-metal-dπ orbitals, showing electronic communication between the metals through the alkynyl bridge. From the photoelectron spectrum, this communication was calculated to have a minimum electron-transfer integral of 0.56 eV. The stabilization of the antisymmetric combination of the metal-metal-dπ orbitals gives a direct and unique experimental measure of the interaction with the alkynyl π orbitals. The stabilization caused by the alkynyl π orbitals was found to be approximately one-third of the destabilization caused by the filled-filled interaction with the alkynyl π-bonds and about one-fourth to one-third the stabilization provided by back-bonding to a carbonyl ligand.

LanguageEnglish (US)
Pages141-150
Number of pages10
JournalPolyhedron
Volume86
DOIs
StatePublished - Jan 28 2015

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photoelectron spectroscopy
electronic structure
metals
interactions
Photoelectron spectroscopy
Electronic structure
Metals
orbitals
stabilization
molecules
Stabilization
Molecules
ionization
Electrons
destabilization
photoelectrons
communication
ligands
electronics
electrons

Keywords

  • Alkynyl ligand
  • Back-bonding
  • III
  • Metal-metal communication
  • Photoelectron spectroscopy
  • Robin-Day class

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Materials Chemistry
  • Physical and Theoretical Chemistry

Cite this

Experimental measure of metal-alkynyl electronic structure interactions by photoelectron spectroscopy : (η5-C5H5)Ru(CO)2CCMe and [(η5-C5H5)Ru(CO)2]2(μ-CC). / Head, Ashley R.; Renshaw, Sharon K.; Uplinger, Andrew B.; Lomprey, Jeffrey R.; Selegue, John P.; Lichtenberger, Dennis L.

In: Polyhedron, Vol. 86, 28.01.2015, p. 141-150.

Research output: Research - peer-reviewArticle

Head, Ashley R. ; Renshaw, Sharon K. ; Uplinger, Andrew B. ; Lomprey, Jeffrey R. ; Selegue, John P. ; Lichtenberger, Dennis L./ Experimental measure of metal-alkynyl electronic structure interactions by photoelectron spectroscopy : (η5-C5H5)Ru(CO)2CCMe and [(η5-C5H5)Ru(CO)2]2(μ-CC). In: Polyhedron. 2015 ; Vol. 86. pp. 141-150
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abstract = "The gas-phase He I and He II photoelectron spectra of the propynylruthenium molecule CpRu(CO)2CCMe (Cp = η5-C5H5) and the ethynediyldiruthenium molecule [CpRu(CO)2]2(μ-CC) are compared with the spectrum of CpRu(CO)2Cl to experimentally determine electronic structure interactions of the alkynyl ligands with the metal. The spectra indicate that the interaction between the filled metal-dπ and filled alkynyl-π orbitals dominates the metal-alkynyl π electronic structure, mirroring previously characterized CpFe(CO)2 alkynyls. All valence ionizations of the Ru molecules are stabilized with respect to similar Fe compounds, contrary to the common expectation of lower ionization energies with atomic substitution down a column of the periodic table. Ab initio electronic structure calculations suggest that this stabilization traces to the greater inherent electronic relaxation energy associated with removal of Fe 3d electrons compared to removal of Ru 4d electrons. Destabilization of the first two ionization bands of the diruthenium molecule are a result of filled-filled interactions between alkynyl π-bonds with the symmetric combination of metal-metal-dπ orbitals, showing electronic communication between the metals through the alkynyl bridge. From the photoelectron spectrum, this communication was calculated to have a minimum electron-transfer integral of 0.56 eV. The stabilization of the antisymmetric combination of the metal-metal-dπ orbitals gives a direct and unique experimental measure of the interaction with the alkynyl π∗ orbitals. The stabilization caused by the alkynyl π∗ orbitals was found to be approximately one-third of the destabilization caused by the filled-filled interaction with the alkynyl π-bonds and about one-fourth to one-third the stabilization provided by back-bonding to a carbonyl ligand.",
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AU - Head,Ashley R.

AU - Renshaw,Sharon K.

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AU - Lomprey,Jeffrey R.

AU - Selegue,John P.

AU - Lichtenberger,Dennis L.

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N2 - The gas-phase He I and He II photoelectron spectra of the propynylruthenium molecule CpRu(CO)2CCMe (Cp = η5-C5H5) and the ethynediyldiruthenium molecule [CpRu(CO)2]2(μ-CC) are compared with the spectrum of CpRu(CO)2Cl to experimentally determine electronic structure interactions of the alkynyl ligands with the metal. The spectra indicate that the interaction between the filled metal-dπ and filled alkynyl-π orbitals dominates the metal-alkynyl π electronic structure, mirroring previously characterized CpFe(CO)2 alkynyls. All valence ionizations of the Ru molecules are stabilized with respect to similar Fe compounds, contrary to the common expectation of lower ionization energies with atomic substitution down a column of the periodic table. Ab initio electronic structure calculations suggest that this stabilization traces to the greater inherent electronic relaxation energy associated with removal of Fe 3d electrons compared to removal of Ru 4d electrons. Destabilization of the first two ionization bands of the diruthenium molecule are a result of filled-filled interactions between alkynyl π-bonds with the symmetric combination of metal-metal-dπ orbitals, showing electronic communication between the metals through the alkynyl bridge. From the photoelectron spectrum, this communication was calculated to have a minimum electron-transfer integral of 0.56 eV. The stabilization of the antisymmetric combination of the metal-metal-dπ orbitals gives a direct and unique experimental measure of the interaction with the alkynyl π∗ orbitals. The stabilization caused by the alkynyl π∗ orbitals was found to be approximately one-third of the destabilization caused by the filled-filled interaction with the alkynyl π-bonds and about one-fourth to one-third the stabilization provided by back-bonding to a carbonyl ligand.

AB - The gas-phase He I and He II photoelectron spectra of the propynylruthenium molecule CpRu(CO)2CCMe (Cp = η5-C5H5) and the ethynediyldiruthenium molecule [CpRu(CO)2]2(μ-CC) are compared with the spectrum of CpRu(CO)2Cl to experimentally determine electronic structure interactions of the alkynyl ligands with the metal. The spectra indicate that the interaction between the filled metal-dπ and filled alkynyl-π orbitals dominates the metal-alkynyl π electronic structure, mirroring previously characterized CpFe(CO)2 alkynyls. All valence ionizations of the Ru molecules are stabilized with respect to similar Fe compounds, contrary to the common expectation of lower ionization energies with atomic substitution down a column of the periodic table. Ab initio electronic structure calculations suggest that this stabilization traces to the greater inherent electronic relaxation energy associated with removal of Fe 3d electrons compared to removal of Ru 4d electrons. Destabilization of the first two ionization bands of the diruthenium molecule are a result of filled-filled interactions between alkynyl π-bonds with the symmetric combination of metal-metal-dπ orbitals, showing electronic communication between the metals through the alkynyl bridge. From the photoelectron spectrum, this communication was calculated to have a minimum electron-transfer integral of 0.56 eV. The stabilization of the antisymmetric combination of the metal-metal-dπ orbitals gives a direct and unique experimental measure of the interaction with the alkynyl π∗ orbitals. The stabilization caused by the alkynyl π∗ orbitals was found to be approximately one-third of the destabilization caused by the filled-filled interaction with the alkynyl π-bonds and about one-fourth to one-third the stabilization provided by back-bonding to a carbonyl ligand.

KW - Alkynyl ligand

KW - Back-bonding

KW - III

KW - Metal-metal communication

KW - Photoelectron spectroscopy

KW - Robin-Day class

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