Issue 35, 2024

Macrocyclic bis-diphosphenes demonstrating bimetallic exo- and endo-cyclic binding modes

Abstract

Macrocyclic bis-diphosphenes, formally heavier derivatives of macrocyclic azobenzenes, are accessed for the first time. These are synthesised in a reproducible fashion, through the nickel-mediated homocoupling of xanthene-derived NHC-stabilised bis-phosphinidene units. This gives direct access to target macrocyclic bis-diphosphenes 2, featuring exo-cyclic coordinated Ni0 fragments. The endo-cyclic binding mode in 3 is realised by NHC-abstraction using CuCl, so demonstrating two homometallic binding modes for this system. Additionally, reaction with CuCl in acetonitrile yields small amounts of a tetra-metallic NiII/CuI complex, which establishes simultaneous exo- and endo-cyclic metal binding. Fluctional solution state behavior in these systems is explored through variable temperature NMR spectroscopy, in addition to computational bonding analyses, giving the first insights into this novel class of compounds.

Graphical abstract: Macrocyclic bis-diphosphenes demonstrating bimetallic exo- and endo-cyclic binding modes

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Article information

Article type
Edge Article
Submitted
29 May 2024
Accepted
15 Jul 2024
First published
18 Jul 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 14154-14160

Macrocyclic bis-diphosphenes demonstrating bimetallic exo- and endo-cyclic binding modes

L. N. Kreimer and T. J. Hadlington, Chem. Sci., 2024, 15, 14154 DOI: 10.1039/D4SC03516J

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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