Jump to main content
Jump to site search

Issue 18, 2020
Previous Article Next Article

Dialumenes – aryl vs. silyl stabilisation for small molecule activation and catalysis

Author affiliations

Abstract

Main group multiple bonds have proven their ability to act as transition metal mimics in the last few decades. However, catalytic application of these species is still in its infancy. Herein we report the second neutral NHC-stabilised dialumene species by use of a supporting aryl ligand (3). Different to the trans-planar silyl-substituted dialumene (3Si), compound 3 features a trans-bent and twisted geometry. The differences between the two dialumenes are explored computationally (using B3LYP-D3/6-311G(d)) as well as experimentally. A high influence of the ligand's steric demand on the structural motif is revealed, giving rise to enhanced reactivity of 3 enabled by a higher flexibility in addition to different polarisation of the aluminium centres. As such, facile activation of dihydrogen is now achievable. The influence of ligand choice is further implicated in two different catalytic reactions; not only is the aryl-stabilised dialumene more catalytically active but the resulting product distributions also differ, thus indicating the likelihood of alternate mechanisms simply through a change of supporting ligand.

Graphical abstract: Dialumenes – aryl vs. silyl stabilisation for small molecule activation and catalysis

Back to tab navigation

Supplementary files

Article information


Submitted
16 Mar 2020
Accepted
17 Apr 2020
First published
21 Apr 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 4817-4827
Article type
Edge Article

Dialumenes – aryl vs. silyl stabilisation for small molecule activation and catalysis

C. Weetman, A. Porzelt, P. Bag, F. Hanusch and S. Inoue, Chem. Sci., 2020, 11, 4817 DOI: 10.1039/D0SC01561J

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.


Social activity

Search articles by author

Spotlight

Advertisements