Bonding in ring whizzers. I. Photoelectron spectra and molecular orbital calculations for (η5-C6H7)Mn(CO)3, (η5-C7H9)Mn(CO)3, and (η5-C7H7)Mn(CO)3

Thomas H. Whitesides, Dennis L Lichtenberger, Richard A. Budnik

Research output: Contribution to journalArticle

50 Citations (Scopus)

Abstract

A series of calculations, checked by reference to photoelectron spectral (PES) data, is used to interpret the electronic structure and elucidate the principal bonding interactions in a series of cyclic pentadienylmanganese tricarbonyl complexes. A linear correlation is obtained between the calculated eigenvalues and the observed ionization potentials. This correlation suggests that deviations from Koopman's theorem are reasonably constant in these complexes and that the PES data can be adequately assigned by the results of the calculations. Two important conclusions result from this study. (1) The principal bonding interaction between the organic ligand and the metal is due to the interaction of the a′(e1″) level of the pentadienyl moiety with the metal dxz orbital; this interaction is considerably more important than the a″(e1″)-dyz interaction. (2) Calculations indicate a low-lying virtual level in C7H7Mn(CO)3, resulting from the interaction of the π* level with a″(e2″) which may play an important role in the fluxional degenerate rearrangement of this molecule.

Original languageEnglish (US)
Pages (from-to)68-73
Number of pages6
JournalInorganic Chemistry
Volume14
Issue number1
StatePublished - 1975
Externally publishedYes

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Orbital calculations
Molecular orbitals
Carbon Monoxide
Photoelectrons
molecular orbitals
photoelectrons
orbitals
rings
Metals
Ionization potential
interactions
Electronic structure
Ligands
Molecules
ionization potentials
metals
eigenvalues
theorems
electronic structure
deviation

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Bonding in ring whizzers. I. Photoelectron spectra and molecular orbital calculations for (η5-C6H7)Mn(CO)3, (η5-C7H9)Mn(CO)3, and (η5-C7H7)Mn(CO)3. / Whitesides, Thomas H.; Lichtenberger, Dennis L; Budnik, Richard A.

In: Inorganic Chemistry, Vol. 14, No. 1, 1975, p. 68-73.

Research output: Contribution to journalArticle

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N2 - A series of calculations, checked by reference to photoelectron spectral (PES) data, is used to interpret the electronic structure and elucidate the principal bonding interactions in a series of cyclic pentadienylmanganese tricarbonyl complexes. A linear correlation is obtained between the calculated eigenvalues and the observed ionization potentials. This correlation suggests that deviations from Koopman's theorem are reasonably constant in these complexes and that the PES data can be adequately assigned by the results of the calculations. Two important conclusions result from this study. (1) The principal bonding interaction between the organic ligand and the metal is due to the interaction of the a′(e1″) level of the pentadienyl moiety with the metal dxz orbital; this interaction is considerably more important than the a″(e1″)-dyz interaction. (2) Calculations indicate a low-lying virtual level in C7H7Mn(CO)3, resulting from the interaction of the π* level with a″(e2″) which may play an important role in the fluxional degenerate rearrangement of this molecule.

AB - A series of calculations, checked by reference to photoelectron spectral (PES) data, is used to interpret the electronic structure and elucidate the principal bonding interactions in a series of cyclic pentadienylmanganese tricarbonyl complexes. A linear correlation is obtained between the calculated eigenvalues and the observed ionization potentials. This correlation suggests that deviations from Koopman's theorem are reasonably constant in these complexes and that the PES data can be adequately assigned by the results of the calculations. Two important conclusions result from this study. (1) The principal bonding interaction between the organic ligand and the metal is due to the interaction of the a′(e1″) level of the pentadienyl moiety with the metal dxz orbital; this interaction is considerably more important than the a″(e1″)-dyz interaction. (2) Calculations indicate a low-lying virtual level in C7H7Mn(CO)3, resulting from the interaction of the π* level with a″(e2″) which may play an important role in the fluxional degenerate rearrangement of this molecule.

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