Pentadienyl complexes of alkali metals: Structure and bonding

Erick Cerpa, Francisco J. Tenorio, Maryel Contreras, Manuel Villanueva, Hiram I. Beltrán, Thomas Heine, Kelling J. Donald, Gabriel Merino

Research output: Contribution to journalArticlepeer-review

26 Citations (Scopus)


A systematic density functional study of the structure and bonding in the alkali-metal pentadienyl complexes C5H7E (E = Li-Cs) and their analogues derived from the 2,4-dimethylpentadienyl ligand is performed. The bonding in these structures has been analyzed in some detail with reference to molecular orbital analysis, and energy partition analysis, obtained by density functional calculations. An energy decomposition analysis indicates that the electrostatic interaction is the main factor to be considered in the stabilization of the gas-phase complexes we have studied. The stability of the U-shaped minimum energy structure decreases (the potential energy surface becomes more shallow) as the metal atom gets larger. We trace this behavior to a weakening of the metal-ligand binding due to the increasing diffuseness of the metal p orbitais on going down group 1. A significant pyramidalization at the terminal carbons in the coordinate U-shaped structure correlates with the strength of the metal-ligand binding. Initial results for the structural preferences of the complexes in solution for the lithium pentadienyl complex are examined in view of contrary experimental data. There still remains plenty of work to be done in modeling metal complexes in solution, and we suggest a way forward.

Original languageEnglish
Pages (from-to)827-833
Number of pages7
Issue number5
Publication statusPublished - 2008 Mar 10

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry


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