The Valence Electronic Structure of Bridging Methylenes: UV Photoelectron Spectroscopy of ε-Methylenebis(dicarbonyl(η5-cyclopentadienyl)manganese)

David C. Catabro, Dennis L. Lichtenberger, Wolfgang A. Herrmann

Research output: Contribution to journalArticlepeer-review

35 Scopus citations

Abstract

The He I photoelectron spectrum of ε-CH2-[(η5-C5H4CH3)Mn(CO)2]2 in the ionization energy range below 11 eV is reported and compared with the ionizations of (η5-C5H4CH3)Mn(CO)3 and (η5-C5H4CH3)Mn(CO)2(C2H4). Excellent agreement is found between the observed ionizations and the predictions of parameter-free molecular orbital calculations. The valence orbitals of the µ- CH2 group appear to have near ideal matching with the frontier orbitals of the (η5-C5H4CH3)Mn(CO)2 fragments to produce the bonding and stability of this cyclopropane analogue. An effective charge transfer from the metals to the methylene occurs in this interaction which results in a high negative charge on the methylene carbon and formation of a net metal-metal bond. The bonding of the bridging methylene in this complex is also compared with the bonding of a terminal methylene with the analogous (η5-C5H5)Mn(CO)2 species. It is concluded that the formation of the metal-metal bond is an important factor in the greater stability of the bridging system.

Original languageEnglish (US)
Pages (from-to)6852-6855
Number of pages4
JournalJournal of the American Chemical Society
Volume103
Issue number23
DOIs
StatePublished - Nov 1981

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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