Nonlinear (d)10 dicoordinated transition metal complexes
In a cover-featured article, Lando Wolters and Matthias Bickelhaupt have analyzed the bonding mechanism in a series of d10 transition metal complexes ML2 with ADF. There is a subtle interplay between interligand steric (Pauli) repulsion for d10-ML2 complexes, which favors a linear geometry, and π backdonation, which is enhanced by a bent geometry. Understanding the subtleties that cause the bite angle in these complexes to deviate from the expected 180° is important for the rational design of transition metal catalysts.
Orbital level diagrams of linear and bent Pd(CO)2
See also:
teaching exercise on energy decomposition analysis
advanced ADF tutorial on fragment analysis
Nature protocol paper on the activation strain model
L. P. Wolters and F. M. Bickelhaupt, ChemistryOpen, 2, 106-114 (2013), cover picture
Key conceptsADF bonding analysis catalysis inorganic chemistry Relativistic DFT