Electronic structure and bonding in methyl- and perfluoromethyl(pentacarbonyl)manganese Academic Article uri icon


  • Using approximate molecular orbital calculations, we have investigated the electronic structure and bonding of CH3Mn(CO)6 and CF3Mn(CO)5. The appearance of an unexpected additional band in the photoelectron spectra can explain both the apparent reversal in the b2 and e bands of the methyl compound and the increased intensity of the first band in the perfluoromethyl compound. Other experimental evidence, such as the carbon-fluorine force constant of the CF3 group, for which dir(metal)-σ∗(CF3) back-bonding has been proposed as an explanation, can be understood in terms of a donation from an antibonding CF3 orbital and energy stabilization due to the effect of charges on neighboring atom. The influence of the CX3 ligands on the metal ionization potentials and on the carbonyl force constants can also be interpreted in terms of these two effects. © 1972, American Chemical Society. All rights reserved.

altmetric score

  • 3

author list (cited authors)

  • Hall, M. B., & Fenske, R. F.

citation count

  • 404

publication date

  • April 1972