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

Rocchigiani, L., 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
Related URLs:
Depositing User: LivePure Connector
Date Deposited: 18 Jun 2019 15:30
Last Modified: 18 Sep 2020 00:22
URI: https://ueaeprints.uea.ac.uk/id/eprint/71463
DOI: 10.1016/j.jorganchem.2012.02.011

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