Bent ML2 Complexes

  • ChemPubSoc Europe Logo
  • Author: Saskia Neubacher
  • Published Date: 27 August 2013
  • Source / Publisher: ChemistryOpen/Wiley-VCH
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
thumbnail image:  Bent ML<sub>2</sub> Complexes

Related Societies

Lando P. Wolters and F. Matthias Bickelhaupt, VU University, The Netherlands, show that not all d10-ML2 complexes are linear. They investigated the molecular geometries and electronic structure of a series of d10-ML2 complexes (M = Co, Rh, Ir, Ni, Pd, Pt, Cu+, Ag+, Au+; L = NH3, PH3, CO) by using relativistic density functional theory (DFT).

By analyzing the bonding mechanism in ML2 as a function of the ligand-metal-ligand (L-M-L) angle with quantitative Kohn–Sham molecular orbital (MO) theory in combination with an energy decomposition analysis (EDA) scheme, they show that the L-M-L angle can vary. Necessary for the occurrence of bent d10-ML2 complexes is sufficiently strong π backdonation. Smaller angles increase the overlap of the ligand’s acceptor orbital with a higher-energy donor orbital on the metal–ligand fragment and, therefore, favor π backdonation, resulting in additional stabilization. The balance between the additional stabilization and the increased steric repulsion, occurring as the complexes are bent, determines the resulting angle of the complex.

The analyses explain the phenomenon and provide a tool for rationally tuning the bite angle.

Article Views: 2682

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, please contact us first for permission. more

CONNECT: on Facebook on Twitter on YouTube on LinkedIn Sign up for our free newsletter

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