Octacarbonyl Anion Complexes of the Late Lanthanides

  • ChemPubSoc Europe Logo
  • Author: Chemistry – A European Journal
  • Published Date: 11 March 2019
  • Source / Publisher: Chemistry – A European Journal/Wiley-VCH
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA
thumbnail image: Octacarbonyl Anion Complexes of the Late Lanthanides

Related Societies

The octet rule for main-group elements and the 18-electron rule for transition metals are useful tools in modern chemistry to rationalize and predict the structure of molecules. They were suggested along with the 32-electron rule for the lanthanides and actinides almost 100 years ago, prior to modern quantum theory. These rules are valid for a large majority of stable molecules.


Lili Zhao, Nanjing Tech University, China, Gernot Frenking, Nanjing Tech University and University of Marburg, Germany, Mingfei Zhao, Fudan University, Shanghai, China, and colleagues have examined the validity of these heuristic rules for the structure and stability of molecules. The researchers studied the late lanthanide complexes [Ln(CO)8] (Ln = Tm, Yb, Lu) using density functional theory (DFT) calculations. Simple counting of the electrons in these complexes gives 32 (Tm), 33 (Yb) and 34 (Lu) valence electrons, respectively.


The nature of the metal–CO interactions has been analyzed using calculations with an energy decomposition method. This method provides qualitative and quantitative insights into the interatomic interactions. The picture above, for example, shows charge flow from the metal d orbital (red region) to the CO ligands (blue region) in [Lu(CO)8]. It was possible to show that the 32-electron rule applies to all three systems if only those electrons that actually occupy the valence orbitals of the metal are considered.


 

Article Views: 408

Sign in Area

Please sign in below

Additional Sign In options

Please note that to comment on an article you must be registered and logged in.
Registration is for free, you may already be registered to receive, e.g., the newsletter. When you register on this website, please ensure you view our terms and conditions. All comments are subject to moderation.

Article Comments - To add a comment please sign in

Bookmark and Share

If you would like to reuse any content, in print or online, from ChemistryViews.org, please contact us first for permission. more


CONNECT:

ChemistryViews.org on Facebook

ChemistryViews.org on Twitter ChemistryViews.org on YouTube ChemistryViews.org on LinkedIn Sign up for our free newsletter


A product of ChemPubSoc Europe (16 European Chemical Societies)and Wiley-VCH