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RESEARCH ARTICLE (Open Access)
Contents Vol 78(6)

closo-Borate aryliodonium zwitterions: convenient intermediates for functional closo-borane derivatives and molecular materials

Piotr Kaszyński https://orcid.org/0000-0002-2325-8560 A B C *
+ Author Affiliations
- Author Affiliations

A Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, PO-90-363 Łódź, Poland.

B Faculty of Chemistry, University of Łódź, PO-91-403 Łódź, Poland.

C Department of Chemistry, Middle Tennessee State University, Murfreesboro, TN 37132, USA.




Piotr Kaszyński is a professor of chemistry at the Centre of Molecular and Macromolecular Studies of the Polish Academy of Sciences and University of Łódź in Poland. He received his MSc degree from Warsaw Polytechnic in Poland in 1985, PhD degrees from the University of Texas at Austin in 1991 and the University of Łodź in 2007. He was a postdoctoral fellow at Caltech before joining Vanderbilt University in Nashville. In 2015, he moved the bulk of his research program to Polish Academy of Sciences and University of Łódź, while maintaining ties with Middle Tennessee State University in USA. He has published over 200 original papers, and several book chapters and reviews.
* Correspondence to: piotr.kaszynski@cbmm.lodz.pl

Handling Editor: Curt Wentrup

Australian Journal of Chemistry 78, CH25006 https://doi.org/10.1071/CH25006
Submitted: 13 January 2025  Accepted: 12 April 2025  Published online: 4 June 2025

© 2025 The Author(s) (or their employer(s)). Published by CSIRO Publishing. This is an open access article distributed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License (CC BY-NC-ND)

Abstract

Zwitterionic aryliodonium derivatives of closo-borates are attractive intermediates in regioselective functionalization of anionic boron clusters through nucleophilic substitution with halides, and N-, O- and C-centered reagents. They are easily available in high yields by highly regioselective direct aryliodination of the closo-borate anions with ArIII species, typically PhI(OAc)2 and undergo four types of transformations: substitution through a rearrangement of a 10-I-3 species, dissociation to boronium ylides and trapping with the solvent, single electron transfer and homolysis of the 9-I-2 species to B–I products, and iodoaryl slippage to cage arylation byproducts. These zwitterions exhibit moderate and well-balanced thermal stability, which, in most cases, is sufficient for their isolation and synthetic applications. It depends on the closo-borane, position of the aryliodonium substituent, the presence of other substituents and finally the nature of the aryl group. The two-step process, aryliodination and substitution, can be regarded as a regioselective activation of the B–H bond for nucleophilic substitution. This review summarizes the formation, structure, stability and reactions of zwitterionic derivatives of 10- and 12-vertex closo-borate anions accumulated in the literature in the past decade.

Keywords: closo-borates, carboranes, functionalization, functional group transformations, hypervalent iodine, iodonium zwitterions, regioselectivity, synthesis.

Biographies

CH25006_B1.gif

Piotr Kaszyński is a professor of chemistry at the Centre of Molecular and Macromolecular Studies of the Polish Academy of Sciences and University of Łódź in Poland. He received his MSc degree from Warsaw Polytechnic in Poland in 1985, PhD degrees from the University of Texas at Austin in 1991 and the University of Łodź in 2007. He was a postdoctoral fellow at Caltech before joining Vanderbilt University in Nashville. In 2015, he moved the bulk of his research program to Polish Academy of Sciences and University of Łódź, while maintaining ties with Middle Tennessee State University in USA. He has published over 200 original papers, and several book chapters and reviews.

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