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Issue 28, 2012
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Relativistic ring currents in metallabenzenes: an analysis in terms of contributions of localised orbitals

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Abstract

Ring currents calculated in the ipsocentric CTOCD-DZ formalism are presented for four representative metallabenzenes, compounds in which a benzene CH group is formally replaced by a transition metal atom with ligands. Aromaticity is probed using ring currents computed using non-relativistic and relativistic orbitals (derived with relativistic effective core potentials or ZORA). Maps computed at different levels of relativistic theory turn out to be similar, showing that orbital nodal character is the main determinant of ring current. Diatropic/paratropic global ring currents in these compounds, and also circulations localised on the metal centre, are interpreted in terms of contributions of localised π-type orbitals and metal d-orbitals, respectively. All four considered metallabenzenes should be regarded as 6π electron species, despite the fact that three support diatropic (‘aromatic’) ring currents and one a paratropic (‘anti-aromatic’) current. The current-density maps determine the correct way to count electrons in these species: differential occupation of d-orbitals of formal π-symmetry contributes to circulation on the metal centre, but not around the benzenoid ring. The overall trend from strongly diatropic to weakly paratropic ring currents along the series 1 to 4 is explained by the increasing strength of interaction between formally non-bonding orbitals on the metal centre and C5H5 moiety, which together make up the six-membered ring.

Graphical abstract: Relativistic ring currents in metallabenzenes: an analysis in terms of contributions of localised orbitals

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Publication details

The article was received on 29 Feb 2012, accepted on 09 May 2012 and first published on 10 May 2012


Article type: Paper
DOI: 10.1039/C2CP40647K
Phys. Chem. Chem. Phys., 2012,14, 9897-9905

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    Relativistic ring currents in metallabenzenes: an analysis in terms of contributions of localised orbitals

    R. W. A. Havenith, F. De Proft, L. W. Jenneskens and P. W. Fowler, Phys. Chem. Chem. Phys., 2012, 14, 9897
    DOI: 10.1039/C2CP40647K

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