An NMR study on the reaction of substituted dimethyl zirconocenes with dimethylanilinium borate

Rocchigiani, L. ORCID: https://orcid.org/0000-0002-2679-8407, Bellachioma, G., Zuccaccia, C. and MacChioni, A. (2012) An NMR study on the reaction of substituted dimethyl zirconocenes with dimethylanilinium borate. Journal of Organometallic Chemistry, 714. pp. 32-40. ISSN 0022-328X

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Abstract

The reaction of a series of dimethyl zirconocenes [Me2Si(Cp)2ZrMe2, 1; Cpt−bu2ZrMe2, 2; Cpn−bu2ZrMe2, 3; Ind2ZrMe2, 4; CpMe42ZrMe2, 5; Cp∗2ZrMe2, 6] with [HNMe2Ph][B(C6F5)4] was investigated by means of NMR spectroscopy. It was found that protonolysis of a Zr–Me group occurred generating a coordinative vacancy at the metal center and methane. Cations coming from 1–4 dimethyl precursors bound NMe2Ph, liberated from the protonation process, and formed zirconaaziridinium ion pairs {[Me2Si(Cp)2Zr(η2–CH2NMePh)][B(C6F5)4], 7; [Cpt−bu2Zr(η2–CH2NMePh)][B(C6F5)4], 8; [Cpn−bu2Zr(η2–CH2NMePh)][B(C6F5)4], 9; [Ind2Zr(η2–CH2NMePh)][B(C6F5)4], 10}, reasonably as a consequence of CH activation of one Me group of coordinated NMe2Ph and methane elimination. The intramolecular/interionic structures and dynamics of 7–10 ion pairs were investigated by 1H, 13C and 19F 1D-and 2D-NMR techniques. The reactions of 7 and 10 ion pairs with 2-methyl-1-heptene afforded stable diastereoisomeric ion pairs bearing a five-member azametallacycle.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
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Depositing User: LivePure Connector
Date Deposited: 18 Jun 2019 15:30
Last Modified: 22 Oct 2022 04:52
URI: https://ueaeprints.uea.ac.uk/id/eprint/71463
DOI: 10.1016/j.jorganchem.2012.02.011

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