Modulation of stacking interactions by transition-metal coordination: ab initio benchmark studies

Mutter, Shaun Thomas and Platts, James Alexis ORCID: https://orcid.org/0000-0002-1008-6595 2010. Modulation of stacking interactions by transition-metal coordination: ab initio benchmark studies. Chemistry - A European Journal 16 (18) , pp. 5391-5399. 10.1002/chem.200902813

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Abstract

A series of ab initio calculations are used to determine the CHπ and ππ-stacking interactions of aromatic rings coordinated to transition-metal centres. Two model complexes have been employed, namely, ferrocene and chromium benzene tricarbonyl. Benchmark data obtained from extrapolation of MP2 energies to the basis set limit, coupled with CCSD(T) correction, indicate that coordinated aromatic rings are slightly weaker hydrogen-bond acceptors but are significantly stronger hydrogen-bond donors than uncomplexed rings. It is found that ππ stacking to a second benzene is stronger than in the free benzene dimer, especially in the chromium case. This is assigned, by use of energy partitioning in the local correlation method, to dispersion interactions between metal d and benzene π orbitals. The benchmark data is also used to test the performance of more efficient theoretical methods, indicating that spin-component scaling of MP2 energies performs well in all cases, whereas various density functionals describe some complexes well, but others with errors of more than 1 kcal mol−1.

Item Type:	Article
Status:	Published
Schools:	Advanced Research Computing @ Cardiff (ARCCA) Chemistry
Subjects:	Q Science > QD Chemistry
Uncontrolled Keywords:	ab initio calculations ; Hydrogen bonds ; Mtallocenes ; Stacking interactions ; Transition metals
Publisher:	Wiley-Blackwell
ISSN:	1521-3765
Last Modified:	18 Oct 2022 13:09
URI:	https://orca.cardiff.ac.uk/id/eprint/12550

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