We use cookies to distinguish you from other users and to provide you with a better experience on our websites. Close this message to accept cookies or find out how to manage your cookie settings. Learn more about our Privacy Notice... [opens in a new tab]

Influence of Pnictogen and Ligand Framework on the Lewis Acidity and Steric Environment in Pnictogen Pincer Complexes

02 September 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Pnictogen pincer complexes are a fascinating class of compounds due to their dynamic molecular and electronic structures, and valuable stoichiometric or catalytic reactivity. As recognition of their unique chemistry has grown, so too has the library of pincer ligands employed and pnictogen centres engaged to prepare them. Here we computationally study how the choice of pincer ligand framework and pnictogen influence the electronic and steric outcomes of the complexes obtained. The most relevant electronic parameter is the pnictogen-centred electrophilicity, which has been quantified by fluoride ion affinities and LUMO energies, while the most relevant steric parameter is the crowding around the central pnictogen, which has been quantified by the %Vbur values and visualized using steric maps. The resulting trends are analyzed with reference to binding pocket size, acceptor orbital type, electronic delocalization, π-donor strengths, and heteroatom incorporation. Thus, considering 16 ligand frameworks and 4 heavy pnictogen centres, this study provides a broad-spectrum view of stereo-electronic variation in pnictogen pincer complexes, which, together with a recent study on geometric variation in the same family, provides a substantial dataset to guide future molecular design and reactivity studies.

Keywords

pnictogen
pincer ligand
p-block
phosphorus
arsenic
antimony
bismuth

Supplementary materials

Title
Description
Actions
Title
Supporting Information
Description
Supporting Information for Manuscript.
Actions

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.