Jump to main content
Jump to site search

Issue 29, 2019

Electrostatic polarization of nonpolar substrates: a study of interactions between simple cations and Mo-bound N2

Author affiliations

Abstract

Although a great deal of catalytic studies have focused on covalent interactions between substrates and catalyst centers, recognition of the importance of noncovalent and ionic interactions is driving new approaches to catalyst design. Electrostatic interactions with simple cations (those with little covalency, such as alkali metals) play crucial roles in many catalytic processes, but these effects are challenging to study due to their complicated solvation and speciation behaviour. These effects are particularly difficult to study during cation-mediated reactions with weakly-polar or non-polar substrates. Dinitrogen is one of the most nonpolar substrates known to be affected by electrostatic interactions in both heterogeneous and homogeneous reactions but understanding the significance of these effects requires further exploration. To examine these effects systematically, a new multidentate ligand framework bearing pendent crown ethers has been developed and incorporated into a series of Mo(0)-based dinitrogen complexes. Prepared via both reduction and ligand substitution routes, the strength and impact of cation–N2 interactions have been studied experimentally (IR spectroscopy) and computationally. Although the smallest cation (Li+) has the largest impact on the ground-state heterobimetallic activation of N2, solvation interactions are highly competitive and result in low Li+–(N2)Mo binding affinities. Thus, although smaller cations can have the largest electronic impact on substrates, these interactions are also the least persistent.

Graphical abstract: Electrostatic polarization of nonpolar substrates: a study of interactions between simple cations and Mo-bound N2

Supplementary files

Article information


Submitted
16 Apr 2019
Accepted
28 May 2019
First published
24 Jun 2019

Dalton Trans., 2019,48, 11004-11017
Article type
Paper
Author version available

Electrostatic polarization of nonpolar substrates: a study of interactions between simple cations and Mo-bound N2

L. G. Pap, A. Couldridge, N. Arulsamy and E. Hulley, Dalton Trans., 2019, 48, 11004 DOI: 10.1039/C9DT01606F

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

Search articles by author

Spotlight

Advertisements