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Deformation density and energy decomposition to describe interactions between (η5-C5H5)M and highly reactive molecules C4H4 and (C3H3)−

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Abstract

Using DFT calculations, an energy decomposition analysis (EDA) combined with natural orbitals for chemical valence (NOCV), EDA-NOCV approach was used to describe the nature of the interaction between η5-cyclopentadienyl metal complexes (η5–C5H5)M, with M=Co, Rh, and cyclobutadiene (Cb) and cyclopropenyl anion (C3H3)− molecules, which are highly reactive molecules in their free state. EDA-NOCV draws a covalent picture for these interactions. With this interpretation of interactions, the character of aromaticity could be the result of the delocalization of six electrons in π orbitals of the (η5–C5H5)M fragment and Cb/C3H3 −1 ligand. This description of the bonding interaction might also justify the experimental observation that, in complexes of CpM-Cb (M=Co, Rh), the viability of the Friedel-Crafts acylation and other electrophilic substitutions on the four-membered ring is greater than that of the five-membered ring.

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Acknowledgments

M. acknowledges the Iranian Ministry of Science and Technology for sponsoring her sabbatical leave. The calculations were carried out by the Erwin Computing Center in Philipps-Universität Marburg (Germany). We are deeply grateful to Prof. G. Frenking for supporting this work.

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  1. Chemistry Department, College of Sciences, Shiraz University, 71454, Shiraz, Iran

    Masoumeh Mousavi & Ali H. Pakiari

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  1. Masoumeh Mousavi
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  2. Ali H. Pakiari
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Correspondence to Masoumeh Mousavi.

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Mousavi, M., Pakiari, A.H. Deformation density and energy decomposition to describe interactions between (η5-C5H5)M and highly reactive molecules C4H4 and (C3H3)− . J Mol Model 20, 2418 (2014). https://doi.org/10.1007/s00894-014-2418-y

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  • DOI: https://doi.org/10.1007/s00894-014-2418-y

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