Unusual hafnium-pyridylamido/ERn heterobimetallic adducts (ERn=ZnR2 or AlR3)

Rocchigiani, Luca, Busico, Vincenzo, Pastore, Antonello, Talarico, Giovanni and Macchioni, Alceo (2014) Unusual hafnium-pyridylamido/ERn heterobimetallic adducts (ERn=ZnR2 or AlR3). Angewandte Chemie - International Edition, 53 (8). pp. 2157-2161. ISSN 1433-7851

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Abstract

NMR spectroscopy and DFT studies indicate that the Symyx/Dow Hf(IV)–pyridylamido catalytic system for olefin polymerization, [{N−,N,CNph−}HfMe][B(C6F5)4] (1, Nph=naphthyl), interacts with ERn (E=Al or Zn, R=alkyl group) to afford unusual heterobimetallic adducts [{N−,N}HfMe(μ‐CNph)(μ‐R)ERn−1][B(C6F5)4] in which the cyclometalated Nph acts as a bridge between Hf and E. 1H VT (variable‐temperature) EXSY NMR spectroscopy provides direct evidence of reversible alkyl exchanges in heterobimetallic adducts, with ZnR2 showing a higher tendency to participate in this exchange than AlR3. 1‐Hexene/ERn competitive reactions with 1 at 240 K reveal that the formation of adducts is strongly favored over 1‐hexene polymerization. Nevertheless, a slight increase in the temperature (to >265 K) initiates 1‐hexene polymerization.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
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Depositing User: LivePure Connector
Date Deposited: 19 Jun 2019 08:30
Last Modified: 18 Sep 2020 00:22
URI: https://ueaeprints.uea.ac.uk/id/eprint/71481
DOI: 10.1002/anie.201308370

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