Issue 8, 2023

Reactivity of tetrel functionalized heptapnictogen clusters towards heteroallenes

Abstract

Despite being known for decades, the solution-state molecular chemistry of heptapnictogen ([Pn7]3−; Pn = P, As) clusters is not well established. Here we study heavy element derivatives of tetrel functionalized heptapnictogen clusters towards heteroallene capture, specifically isocyanates, an isothiocyanate and CO2 are probed. Clusters (Me3Ge)3P7 (1), (Et3Ge)3P7 (2), (nBu3Sn)3P7 (3), and (Me3Si)3As7 (4) were all found to capture isocyanates between all three of their tetrel–pnictogen bonds. In the case of phenyl isocyanate insertion, tetrel coordination at the isocyanate nitrogen atoms is preferred, while in the case of p-toluenesulfonyl isocyanate insertion, tetrel coordination at oxygen is preferred. Furthermore, the reaction of (Me3Si)3P7 with CO2 gave NMR spectra consistent with the capture of the greenhouse gas. Heteroallene insertion at these clusters was also studied using density functional theory.

Graphical abstract: Reactivity of tetrel functionalized heptapnictogen clusters towards heteroallenes

Supplementary files

Article information

Article type
Paper
Submitted
20 12 2022
Accepted
23 1 2023
First published
31 1 2023
This article is Open Access
Creative Commons BY license

Dalton Trans., 2023,52, 2384-2391

Reactivity of tetrel functionalized heptapnictogen clusters towards heteroallenes

W. D. Jobbins, B. van IJzendoorn, I. J. Vitorica-Yrezabal, G. F. S. Whitehead and M. Mehta, Dalton Trans., 2023, 52, 2384 DOI: 10.1039/D2DT04074C

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