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{Rh(PiBu3)2}+ Fragments Ligated to Arenes: From Benzene to Polyaromatic Hydrocarbons, Part II – Computational Analysis of Pathways for Haptotropic Migration

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  • Part I: Ref.1

Abstract

Density functional theory has been used to probe the structures and solution dynamics of a series of polyaromatichydrocarbon complexes of the 12-electron fragment {Rh(PiBu3)2}+. These studies suggest that the strength of the binding of the metal to the hydrocarbon surface is controlled by the electronic demands of both the metal (16-electron configuration) and ligand (maximum retention of aromaticity). In cases where these two factors can be satisfied simultaneously an energetically isolated equilibrium structure emerges and haptotropic shifts are blocked. In cases where a compromise between the requirements of the metal and ligand is unavoidable the potential energy surface is rather flatter, leading to rapid haptotropic shifts between near iso-energetic isomers.

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