Zirconium arene triple-decker sandwich complexes: synthesis, electronic structure and bonding. Issue 88 (24th October 2017)

• Record Type: Journal Article
• Authors: Kilpatrick, A. F. R.; Green, J. C.; Turner, Z. R.; Buffet, J.-C.; O'Hare, D.
• Is Part Of: Chemical communications. Volume 53:Issue 88(2017)
• Page Start: 12048
• Page End: 12051
• Publication Date: 2017-10-24
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/c7cc07083g
• Languages: English
• ISSNs: 1359-7345

Abstract

Abstract : Reduction of a permethylpentalene zirconium(iv ) chloride complex [η 8 -Pn*Zr(μ-Cl)3/2 ]2 (μ-Cl)2 Li·THF x with KC8 in benzene results in activation of the aromatic solvent to yield an "inverted sandwich" complex, [η 8 -Pn*Zr]2 (μ-η 6 :η 6 -C6 H6 ) (1 ). Abstract : Reduction of a permethylpentalene zirconium(iv ) chloride complex [η 8 -Pn*Zr(μ-Cl)3/2 ]2 (μ-Cl)2 Li·THF x with KC8 in benzene results in activation of the aromatic solvent to yield an "inverted sandwich" complex, [η 8 -Pn*Zr]2 (μ-η 6 :η 6 -C6 H6 ) (1 ). The 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 between1 and formally Zr(ii ) and Zr(iv ) reference compounds, suggesting a broad edge structure. DFT calculations best describe the bonding in1 as highly covalent with frontier molecular orbitals showing almost equal contributions from benzene and the Zr-permethylpentalene fragments.