Copper(ii) complexes of N-propargyl cyclam ligands reveal a range of coordination modes and colours, and unexpected reactivity
- 21 March 2021
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Dalton Transactions
- Vol. 50 (11), 3931-3942
- https://doi.org/10.1039/d0dt03736b
Abstract
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.Other Versions
Funding Information
- Australian Government
- Australian Research Council (DP120104035)
This publication has 74 references indexed in Scilit:
- Supramolecular Luminescent SensorsChemical Reviews, 2018
- Review on Recent Advances in Metal Ions Sensing Using Different Fluorescent ProbesJournal of Fluorescence, 2018
- Molecular Switches for any pH: A Systematic Study of the Versatile Coordination Behaviour of Cyclam ScorpionandsChemistry – A European Journal, 2017
- A Robust Open Framework Formed by Decavanadate Clusters and Copper(II) Complexes of Macrocyclic Polyamines: Permanent Microporosity and Catalytic Oxidation of CycloalkanesInorganic Chemistry, 2016
- Cyclams with Ambidentate Methylthiazolyl Pendants for Stable, Inert, and Selective Cu(II) CoordinationInorganic Chemistry, 2015
- Monoesterase Activity of a Purple Acid Phosphatase Mimic with a Cyclam PlatformChemistry – A European Journal, 2012
- Coordination chemistry of N-tetraalkylated cyclam ligands—A status reportCoordination Chemistry Reviews, 2010
- Light-Emitting Molecular Machines: pH-Induced Intramolecular Motions in a Fluorescent Nickel(II) Scorpionate ComplexChemistry – A European Journal, 2002
- New Iron(II) and Manganese(II) Complexes of Two Ultra-Rigid, Cross-Bridged Tetraazamacrocycles for Catalysis and BiomimicryJournal of the American Chemical Society, 2000
- Synthesis and metal complexes of aza-macrocycles with pendant arms having additional ligating groupsPublished by Springer Science and Business Media LLC ,1984