Issue 24, 2020

α-C–C agostic interactions and C–H bond activation in scandium cyclopropyl complexes

Abstract

This paper addresses the problem of the observation of the so-called C–C agostic interactions in cyclopropyl complexes of scandium. Three new cyclopropyl complexes of scandium based on the β-diketiminato ligand were synthesized including by an intramolecular C–H bond activation reaction in one case. X-ray diffraction analysis revealed distorted cyclopropyl groups in the complexes, and the distortion could be observed in solution as well for one of the complexes thanks to the natural abundance INADEQUATE NMR spectroscopy which showed a markedly reduced JC–C coupling constant. This signature of the C–C agostic interaction was further examined using DFT modelling which, together with NBO calculations, indicated that C–H and C–C agostic interactions are not exclusive but can complement each other, accounting for the distortions. The intramolecular C–H bond activation in the scandium biscyclopropyl complex was investigated by isotopic labeling experiments, which indicated a direct proton abstraction of the isopropyl group in the β-diketiminato ligand by a cyclopropyl group.

Graphical abstract: α-C–C agostic interactions and C–H bond activation in scandium cyclopropyl complexes

Supplementary files

Article information

Article type
Research Article
Submitted
25 Sep 2020
Accepted
06 Nov 2020
First published
06 Nov 2020

Inorg. Chem. Front., 2020,7, 4822-4831

α-C–C agostic interactions and C–H bond activation in scandium cyclopropyl complexes

C. Xu, G. Li, M. Etienne, X. Leng and Y. Chen, Inorg. Chem. Front., 2020, 7, 4822 DOI: 10.1039/D0QI01163K

To request permission to reproduce material from this article, 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 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

Spotlight

Advertisements