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

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dc.contributor.authorCounsell, A.J.
dc.contributor.authorYu, M.
dc.contributor.authorShi, M.
dc.contributor.authorJones, A.T.
dc.contributor.authorBatten, J.M.
dc.contributor.authorTurner, P.
dc.contributor.authorTodd, M.H.
dc.contributor.authorRutledge, P.J.
dc.date.issued2021
dc.descriptionData source: Supplementary information, https://doi.org/10.1039/D0DT03736B
dc.description.abstractThe 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.
dc.identifier.citationDalton Transactions, 2021; 50(11):3931-3942
dc.identifier.doi10.1039/d0dt03736b
dc.identifier.issn1477-9226
dc.identifier.issn1477-9234
dc.identifier.urihttps://hdl.handle.net/11541.2/147992
dc.language.isoen
dc.publisherRoyal Society of Chemistry
dc.relation.fundingUniversity of Sydney International Scholarship (USydIS)
dc.relation.fundingResearch Training Program (RTP) Scholarship from the Australian Government
dc.relation.fundingARC DP120104035
dc.rightsCopyright 2021 Royal Society of Chemistry
dc.source.urihttps://doi.org/10.1039/d0dt03736b
dc.subjectcopper (II)
dc.subjectN-propargyl
dc.subjectcyclam
dc.subjectligands
dc.titleCopper(ii) complexes of N-propargyl cyclam ligands reveal a range of coordination modes and colours, and unexpected reactivity
dc.typeJournal article
pubs.publication-statusPublished
ror.mmsid9916505397001831

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