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How Much Electron Donation Is There In Transition Metal Complexes? A Computational Study.
Augustine Obeng1, Jochen Autschbach1
1Department of Chemistry, University at Buffalo State University of New York Buffalo, New York 14260-3000, United States.
Journal of Chemical Theory and Computation
|June 10, 2024
Summary
This study evaluates computational methods for accurately describing dative bonding in metal complexes. Certain density functionals and coupled-cluster models show promise for quantifying metal-ligand electron donation.
Area of Science:
- Computational Chemistry
- Quantum Chemistry
- Coordination Chemistry
Background:
- Dative covalent interactions (metal-to-ligand and ligand-to-metal donation) are crucial in coordination chemistry.
- Electron delocalization in these interactions is challenging for approximate computational methods.
- Accurate description of dative bonding is essential for understanding chemical reactivity and properties.
Purpose of the Study:
- To assess the accuracy of various computational methods in quantifying dative bonding in closed-shell transition metal complexes.
- To identify reliable theoretical approaches for describing metal-ligand electron donation.
- To compare the performance of different density functionals and post-Hartree-Fock methods.
Main Methods:
- Assessment of Kohn-Sham density functionals across different approximation "rungs".
- Evaluation of post-Hartree-Fock methods, including MP2 and coupled-cluster models.
- Benchmarking against the coupled cluster singles and doubles with perturbative triples (CCSD(T)) reference method.
Main Results:
- Nonhybrid and global hybrid functionals (e.g., B3LYP, PBE0) often overestimate dative donation.
- Global hybrids with higher exact exchange (40-50%) and CAM-B3LYP show improved accuracy.
- Double-hybrid functionals provide satisfactory results, correcting MP2 errors.
- DLPNO-CCSD offers a reasonable, though slightly underestimating, description of donation.
Conclusions:
- The choice of computational method significantly impacts the accuracy of dative bonding descriptions.
- Range-separated and double-hybrid functionals, along with approximate coupled-cluster methods, represent promising avenues for accurate dative interaction calculations.
- Further refinement of computational models is needed for precise quantification of electron donation in coordination complexes.
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