Potassium Aluminyl Promoted Carbonylation of Ethene

Matthew J. Evans, Samuel E. Neale, Mathew D. Anker, Claire L. McMullin, Martyn P. Coles

Research output: Contribution to journalArticlepeer-review

15 Citations (SciVal)

Abstract

The potassium aluminyl [K{Al(NONDipp)}]2 ([NONDipp]2−=[O{SiMe2NDipp}2]2−, Dipp=2,6-iPr2C6H3) activates ethene towards carbonylation with CO under mild conditions. An isolated bis-aluminacyclopropane compound reacted with CO via carbonylation of an Al−C bond, followed by an intramolecular hydrogen shift to form K2[Al(NONDipp)(μ-CH2CH=CO-1κ2C1,3-2κO)Al(NONDipp)Et]. Restricting the chemistry to a mono-aluminium system allowed isolation of [Al(NONDipp)(CH2CH2CO-κ2C1,3)], which undergoes thermal isomerisation to form the [Al(NONDipp)(CH2CH=CHO-κ2C,O)] anion. DFT calculations highlight the stabilising influence of incorporated benzene at multiple steps in the reaction pathways.

Original languageEnglish
Article numbere202117396
JournalAngewandte Chemie-International Edition
Volume61
Issue number16
Early online date14 Feb 2022
DOIs
Publication statusPublished - 11 Apr 2022

Bibliographical note

Funding Information:
This research made use of the Rāpoi (Victoria University of Wellington) and Balena (University of Bath) High Performance Computing (HPC) services. Open access publishing facilitated by Victoria University of Wellington, as part of the Wiley - Victoria University of Wellington agreement via the Council of Australian University Librarians.

Publisher Copyright:
© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Keywords

  • Aluminyl Anions
  • Bimetallic Complexes
  • Carbonylation
  • Hydrogen-Shift
  • Metallacycles

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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