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DFT study of H--H activation by Cp(2) LnH d(0) complexes.

Authors
  • Maron, L
  • Eisenstein, O
Type
Published Article
Journal
Journal of the American Chemical Society
Publication Date
Feb 14, 2001
Volume
123
Issue
6
Pages
1036–1039
Identifiers
PMID: 11456656
Source
Medline
License
Unknown

Abstract

The energy required to activate the H--H bond in the entire series of Cp(2)LnH complexes has been calculated by DFT (B3PW91) methods. The activation energies have been calculated to vary from 0.5 to 8.0 kcal x mol(-1), indicating an overall facile reaction. The electronegativity of the lanthanide in its most stable oxidation state is suggested to be a leading factor for interpreting the trends in activation energy. The geometry of the transition state is best viewed as an almost linear H(3)(-) ligand with short H--H distances and strong M--H interaction, through the wingtip H centers, with Ln. The exchange reaction is thus established to be a sigma bond metathesis reaction.

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