Potassium Aluminyl Promoted Carbonylation of Ethene.
Potassium Aluminyl Promoted Carbonylation of Ethene.
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DOI：
10.1002/anie.202117396
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发表时间：
2022-04-11
影响因子：
16.6
通讯作者：
Coles, Martyn P.
中科院分区：
文献类型：
--
作者：
Evans, Matthew J.;Neale, Samuel E.;Anker, Mathew D.;McMullin, Claire L.;Coles, Martyn P.
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‐1κ2 C 1,3‐2κO)Al(NONDipp)Et]. Restricting the chemistry to a mono‐aluminium system allowed isolation of [Al(NONDipp)(CH2CH2CO‐κ2 C 1,3)]−, which undergoes thermal isomerisation to form the [Al(NONDipp)(CH2CH=CHO‐κ2 C,O)]− anion. DFT calculations highlight the stabilising influence of incorporated benzene at multiple steps in the reaction pathways. Metal‐promoted carbonylation of alkenes is established for d‐block metals, whilst prior work with aluminium has been limited by reversible C=C coordination and decomposition of CO insertion products. This work shows how the aluminyl anion allows the non‐reversible carbonylation of ethene using carbon monoxide under mild conditions. A bimetallic pathway involving an intramolecular 1,2‐hydrogen shift was identified and supported by DFT calculations.
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影响因子：
64.8
作者：
Hicks, Jamie;Vasko, Petra;Aldridge, Simon
通讯作者：
Aldridge, Simon
DOI：
10.1002/anie.202006693
发表时间：
2020-09-07
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Grams S;Eyselein J;Langer J;Färber C;Harder S
通讯作者：
Harder S
影响因子：
15
作者：
Hicks, Jamie;Vasko, Petra;Aldridge, Simon
通讯作者：
Aldridge, Simon
影响因子：
8.4
作者：
Bakewell, Clare;White, Andrew J. P.;Crimmin, Mark R.
通讯作者：
Crimmin, Mark R.
影响因子：
4.6
作者：
Bakewell, Clare;Garcon, Marti;Crimmin, Mark R.
通讯作者：
Crimmin, Mark R.