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Woolf A.,Inorganic Chemistry Laboratories | Alibadi M.A.M.,Inorganic Chemistry Laboratories | Chaplin A.B.,Inorganic Chemistry Laboratories | McGrady J.E.,Inorganic Chemistry Laboratories | Weller A.S.,Inorganic Chemistry Laboratories
European Journal of Inorganic Chemistry | Year: 2011

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(PiBu 3) 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. Unavoidable compromises between the electronic demands of the {Rh(PiBu 3) 2} + fragment and the aromatic ligand lead to low barriers to haptotropic shifts in complexes of pyrene and coronene. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA.


Woolf A.,Inorganic Chemistry Laboratories | Chaplin A.B.,Inorganic Chemistry Laboratories | McGrady J.E.,Inorganic Chemistry Laboratories | Alibadi M.A.M.,Inorganic Chemistry Laboratories | And 4 more authors.
European Journal of Inorganic Chemistry | Year: 2011

We report the synthesis, structural characterisation andsolution-phase dynamics of a series of polyaromatic hydrocarbon complexes of the 12-electron {Rh(PiBu 3) 2} + fragment. Crystal structures of this fragment with benzene, naphthalene, anthracene, pyrene, triphenylene and coronene are described, alongside their solution NMR spectroscopic data. The ligands map out a systematic increase in size of the aromatic subunit, and represent an approach to the limiting case of coordination to a graphene surface. The solid-state and solution structures of a {Rh(COD)} + fragment coordinated to a hexa-peri-hexabenzocoronene are also reported. A range of polyaromatic hydrocarbons of increasing size (naphthalene through coronene) have been prepared and their solid-state and solution structures investigated. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA.

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