Copper(ii) complexes of N-propargyl cyclam ligands reveal a range of coordination modes and colours, and unexpected reactivity

• Published in: Dalton transactions : an international journal of inorganic chemistry 2021-03, Vol.50 (11), p.3931-3942
• Main Authors: Counsell, Andrew J, Yu, Mingfeng, Shi, Mengying, Jones, Angus T, Batten, James M, Turner, Peter, Todd, Matthew H, Rutledge, Peter J
• Format: Article
• Language: English
• Subjects: Alkynes; Coordination compounds; Copper compounds; Crystal structure; Crystallography; Ligands; Recrystallization; Single crystals
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d0dt03736b

The coordination chemistry of N-functionalised cyclam ligands has a rich history, yet cyclam derivatives with pendant alkynes are largely unexplored. This is despite the significant potential and burgeoning application of N-propargyl cyclams and related compounds in the creation of diversely functionalised cyclam derivatives via copper-catalysed azide-alkyne 'click' reactions. Herein we describe single crystal X-ray diffraction and spectroscopic investigations of the coordination chemistry of copper(ii) complexes of cyclam derivatives with between 1 and 4 pendant alkynes. The crystal structures of these copper complexes unexpectedly reveal a range of coordination modes, and the surprising occurrence of five unique complexes within a single recrystallisation of the tetra-N-propargyl cyclam ligand. One of these species exhibits weak intramolecular copper-alkyne coordination, and another is formed by a surprising intramolecular copper-mediated hydroalkoxylation reaction with the solvent methanol, transforming one of the pendant alkynes to an enol ether. Multiple functionalisation of the tetra-N-propargyl ligand is demonstrated via a 'tetra-click' reaction with benzyl azide, and the copper-binding behaviour of the resulting tetra-triazole ligand is characterised spectroscopically.