Unknown

Dataset Information

0

Reversible alkene binding and allylic C-H activation with an aluminium(i) complex.


ABSTRACT: The monomeric molecular aluminium(i) complex 1 [{(ArNCMe)2CH}Al] (Ar = 2,6-di-iso-propylphenyl) reacts with a series of terminal and strained alkenes including ethylene, propylene, allylbenzene and norbornene to form alkene bound products. Remarkably all these reactions are reversible under mild conditions (298-353 K) with alkene binding being disfavoured at higher temperatures due to the positive reaction entropy. Van't Hoff analyses have allowed quantification of the binding events with . Calculations and single crystal X-ray diffraction studies are consistent with the alkene bound species being metallocyclopropane complexes. Alkene binding involves a reversible redox process with changes from the +1 to +3 aluminium oxidation state. Under more forcing conditions the metallocyclopropane complexes undergo non-reversible allylic C-H bond activation to generate aluminium(iii) allyl hydride complexes. This represents a rare example of redox-based main group reactivity in which reversible substrate binding is followed by a further productive bond breaking event. Analysis of the mechanism reveals a reaction network in which alkene dissociation and reformation of 1 is required for allylic C-H activation, a realisation that has important implications for the long-term goal of developing redox-based catalytic cycles with main group compounds.

SUBMITTER: Bakewell C 

PROVIDER: S-EPMC6388093 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature

altmetric image

Publications

Reversible alkene binding and allylic C-H activation with an aluminium(i) complex.

Bakewell Clare C   White Andrew J P AJP   Crimmin Mark R MR  

Chemical science 20190108 8


The monomeric molecular aluminium(i) complex <b>1</b> [{(ArNCMe)<sub>2</sub>CH}Al] (Ar = 2,6-di-iso-propylphenyl) reacts with a series of terminal and strained alkenes including ethylene, propylene, allylbenzene and norbornene to form alkene bound products. Remarkably all these reactions are reversible under mild conditions (298-353 K) with alkene binding being disfavoured at higher temperatures due to the positive reaction entropy. Van't Hoff analyses have allowed quantification of the binding  ...[more]

Similar Datasets

| S-EPMC6376213 | biostudies-literature
| S-EPMC9573877 | biostudies-literature
| S-EPMC6013809 | biostudies-literature
| S-EPMC4043347 | biostudies-literature
| S-EPMC9159098 | biostudies-literature
| S-EPMC8161683 | biostudies-literature
| S-EPMC8252388 | biostudies-literature
| S-EPMC10558119 | biostudies-literature
| S-EPMC5499723 | biostudies-literature
| S-EPMC3568340 | biostudies-literature