Counterintuitive Consequences of Filled Ligand. Pi. Interactions with Metal D Orbitals

John L. Hubbard, L. Lichtenberger

Research output: Contribution to journalArticlepeer-review

17 Scopus citations


A recent paper305 describes “an interesting dichotomy concerning the ligating properties of NS and NO” in (η306-C5H5)Cr(CO)2NO and -NS complexes. The authors point out that “on the one hand, IR and electron-impact data suggest that NS is a better remover of electron density from the chromium atom than is NO. On the other hand, NMR and ionization potential measurements imply that it is a better provider of electrons to the metal center. A similar contradiction in experimental observations has been reported for the related complexes (η5-C5H5)Mn(CO)2CS and (η5-C5H5)Mn-(CO)3,” From our previous results of valence photoelectron and parameter-free molecular orbital studies of thiocarbonyl complexes, we have shown that the NMR and ionization potential shifts from the carbonyl to the thiocarbo'nyl complexes are not inconsistent with a decrease of electron density at the metal center.307 The important feature is a more strongly interacting x-bonding orbital (bonding between carbon and sulfur) of the CS ligand.

Original languageEnglish (US)
Pages (from-to)3865-3866
Number of pages2
JournalInorganic Chemistry
Issue number12
StatePublished - 1980

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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