Synthesis, crystal structure and reactions of zerovalent 16-electron bis(η-cycloheptatriene)zirconium
- 1 January 1991
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 2,p. 173-180
- https://doi.org/10.1039/dt9910000173
Abstract
Reduction of ZrCl4 with sodium amalgam in the presence of cycloheptatriene gives the crystallographically identified [Zr(η6-C7H8)2]1 which exhibits a non-parallel arrangement of the cycloheptatrienyl ligands. This reacts with PMe3 or 1,2-bis(dimethylphosphino)ethane (dmpe) to yield [Zr(η7-C7H7)(η5-C7H9)(PMe3)]2 and [{Zr(η7-C7H7)(η5-C7H9)}2(dmpe)]3 respectively. Treatment of compound 1 with (AlEt2Cl)2 in tetrahydrofuran (thf) yields [{Zr(η7-C7H7)(thf)(µ-Cl)}2]4 which reacts with N,N,N′,N′-tetramethylethylenediamine, PMe3, dmpe and 1,2-dimethoxyethane to produce [Zr(η7-C7H7)(Me2NCH2CH2NMe2)Cl]5, [Zr(η7-C7H7)(PMe3)2Cl]6, [Zr(η7-C7H7)(dmpe)Cl]7 and [Zr(η7-C7H7)(MeOCH2CH2OMe)Cl]8, respectively. The electronic structures of 1 and [Zr(η7-C7H7)(η5-C7H9)]11 have been investigated by photoelectron spectroscopy and extended-Hückel molecular-orbital calculations.Keywords
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