Potassium Aluminyl Promoted Carbonylation of Ethene

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

doi:10.1002/anie.202117396

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 journal › Article › peer-review

Abstract

The potassium aluminyl [K{Al(NON^Dipp)}]₂ ([NON^Dipp]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(NON^Dipp)(μ-CH₂CH=CO-1κ²C^1,3-2κO)Al(NON^Dipp)Et]. Restricting the chemistry to a mono-aluminium system allowed isolation of [Al(NON^Dipp)(CH₂CH₂CO-κ²C^1,3)]⁻, which undergoes thermal isomerisation to form the [Al(NON^Dipp)(CH₂CH=CHO-κ²C,O)]⁻ anion. DFT calculations highlight the stabilising influence of incorporated benzene at multiple steps in the reaction pathways.

Original language	English
Article number	e202117396
Journal	Angewandte Chemie-International Edition
Volume	61
Issue number	16
Early online date	14 Feb 2022
DOIs	https://doi.org/10.1002/anie.202117396
Publication status	Published - 11 Apr 2022

Keywords

Aluminyl Anions
Bimetallic Complexes
Carbonylation
Hydrogen-Shift
Metallacycles

ASJC Scopus subject areas

Catalysis
Chemistry(all)

Access to Document

10.1002/anie.202117396Licence: CC BY

Cite this

@article{7a1d5cd53a6149768317a266c8dbc56f,

title = "Potassium Aluminyl Promoted Carbonylation of Ethene",

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.",

keywords = "Aluminyl Anions, Bimetallic Complexes, Carbonylation, Hydrogen-Shift, Metallacycles",

author = "Evans, {Matthew J.} and Neale, {Samuel E.} and Anker, {Mathew D.} and McMullin, {Claire L.} and Coles, {Martyn P.}",

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: {\textcopyright} 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

year = "2022",

month = apr,

day = "11",

doi = "10.1002/anie.202117396",

language = "English",

volume = "61",

journal = "Angewandte Chemie-International Edition",

issn = "1433-7851",

publisher = "WILEY-V C H VERLAG GMBH",

number = "16",

}

TY - JOUR

T1 - Potassium Aluminyl Promoted Carbonylation of Ethene

AU - Evans, Matthew J.

AU - Neale, Samuel E.

AU - Anker, Mathew D.

AU - McMullin, Claire L.

AU - Coles, Martyn P.

N1 - 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.

PY - 2022/4/11

Y1 - 2022/4/11

N2 - 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.

AB - 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.

KW - Aluminyl Anions

KW - Bimetallic Complexes

KW - Carbonylation

KW - Hydrogen-Shift

KW - Metallacycles

UR - http://www.scopus.com/inward/record.url?scp=85125104518&partnerID=8YFLogxK

U2 - 10.1002/anie.202117396

DO - 10.1002/anie.202117396

M3 - Article

AN - SCOPUS:85125104518

VL - 61

JO - Angewandte Chemie-International Edition

JF - Angewandte Chemie-International Edition

SN - 1433-7851

IS - 16

M1 - e202117396

ER -

Potassium Aluminyl Promoted Carbonylation of Ethene

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this