Reaktionen von bis(η-cyclopentadienyl)zirconiumhydriden mit (iminoacyl)zirconocen-komplexen |
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Authors: | Wolfgang Frmberg Gerhard Erker |
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Institution: | Abteilung für Chemie der Ruhr-Universität, D 4630 Bochum 1 B.R.D. |
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Abstract: | The reaction of imidoylzirconocene complexes with zirconocene hydrides yields (N-alkylamido)zirconocene complexes. For a mechanistic study, the specifically substituted imidoylzirconocene complexes 3b–3d have been prepared and treated with the oligomeric metal hydrides (Cp2ZrH2)x (1b) and (Cp2ZrHCl)x (1c). (N-Benzyl formimidoyl)zirconocene chloride (3b) was obtained by treating 1c with benzyl isonitrile 2a. Treatment of dimethylzirconocene with 2a gave (N-benzyl acetimidoyl)methylzirconocene (3c), which was treated with PhICl2 to give (N-benzylacetimidoyl)zirconocene chloride (3d). The reaction of 3d with (Cp2ZrH2)x (1b) yielded (N-benzyl-N-ethylamido)zirconocene chloride (4b) as the only identified product. A 1/1 mixture of 4b and methylzirconocene chloride was obtained upon treatment of 3c with (Cp2ZrHCl)x (1c); in contrast, the reaction of 1c with 3b gave an equimolar mixture of Cp2ZrCl2 and (N-benzyl-N-methylamido)zirconocene chloride (4c). Reaction paths through binuclear (μ-CHR′=NR) zirconocene intermediates are proposed to explain these experimental observations. |
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