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Zirconium arene triple-decker sandwich complexes: Synthesis, electronic structure and bonding

DOI: 10.1039/C7CC07083G DOI Help

Authors: Alexander F. R. Kilpatrick (University of Sussex) , Jennifer Green (University of Oxford) , Zoe Turner (University of Oxford) , Jean-charles Buffet (University of Oxford) , Dermot O'hare (University of Oxford)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chem. Commun.

State: Published (Approved)
Published: October 2017
Diamond Proposal Number(s): 15150 , 15521

Abstract: Reduction of a permethylpentalene zirconium(IV) chloride complex [η8-Pn*Zr(μ-Cl)3/2]2(μ-Cl)2Li·THFx with KC8 in benzene results in activation of the aromatic solvent to yield an “inverted sandwich” complex, [η8-Pn*Zr]2(μ-η6:η6-C6H6) (1). The analogous reactions in toluene, cumene, o-xylene and m-xylene also yield analogous solvent activated triple-decker sandwich complexes, which have been structurally characterised by single-crystal X-ray diffraction. Edge energies in the Zr K-edge XANES spectra are not distinguishable between 1 and formally Zr(II) and Zr(IV) reference compounds, suggesting a broad edge structure. DFT calculations best describe the bonding in 1 as highly covalent with frontier molecular orbitals showing almost equal contributions from benzene and the Zr-permethylpentalene fragments.

Subject Areas: Chemistry

Instruments: B18-Core EXAFS

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