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Intramolecular π-stacks in mixed-ligand copper(II) complexes formed by heteroaromatic amines and antivirally active acyclic nucleotide analogs carrying a hydroxy-2-(phosphonomethoxy)propyl residue

Blindauer, Claudia A. and Griesser, Rolf and Holy, Antonin and Operschall, Bert P. and Sigel, Astrid and Song, Bin and Sigel, Helmut. (2018) Intramolecular π-stacks in mixed-ligand copper(II) complexes formed by heteroaromatic amines and antivirally active acyclic nucleotide analogs carrying a hydroxy-2-(phosphonomethoxy)propyl residue. Journal of coordination chemistry, 71 (11-13). pp. 1910-1934.

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Official URL: https://edoc.unibas.ch/68537/

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Abstract

Acyclic nucleoside phosphonates (ANPs) are of medical relevance and deserve detailed chemical characterization. We focus here on 1-[2-(phosphonomethoxy)ethyl]cytosine (PMEC), ( S )-1-[3-hydroxy-2-(phosphonomethoxy)propyl]cytosine (HPMPC), 9-[2-(phosphonomethoxy)ethyl]adenine (PMEA), and ( S )-9-[3-hydroxy-2-(phosphonomethoxy)propyl]adenine (HPMPA) and include for comparison the nucleobase-free (phosphonomethoxy)ethane (PME) and ( R )-hydroxy-2-(phosphonomethoxy)propane (HPMP). The acidity constants of H 3 (ANP) + and H 2 (NP) (NP 2- = nucleoside phosph(on)ate derivative) are needed to understand the properties of the ternary neutral Cu(Arm)(ANP/NP) [Arm = 2,2′-bipyridine (Bpy) or 1,10-phenanthroline (Phen)] and the monoprotonated Cu(Arm)(H;ANP) + complexes. The Cu(Arm)(ANP) species are considerably more stable than the corresponding Cu(Arm)(R-PO 3 ), where R- represents a phosph(on)ate ligand with a non-coordinating group R. The observed stability enhancements are due to intramolecular stack formation (st) between the aromatic rings of Arm and the nucleobase residues and also to the formation of five-membered chelates involving the ether oxygen of the -CH(R)-O-CH 2 - residue (cl/O) (R = H or CH 2 -OH). In intramolecular equilibria, three structurally different Cu(Arm)(ANP) isomers occur; for example, of Cu(Phen)(HPMPA) about 5% exist as an open (op) Cu(Phen)(HPMPA) op isomer, 17% as Cu(Phen)(HPMPA) cl/O , and 78% as Cu(Phen)(HPMPA) st . In Cu(Arm)(ANP) the stacking tendency decreases in the order PMEA 2- > HPMPA 2- > PMEC 2- > HPMPC 2- . In monoprotonated Cu(Arm)(H;ANP) + both H + and Cu(Arm) 2+ are at undergoing similar intramolecular equilibria as indicated above.
Faculties and Departments:05 Faculty of Science > Departement Chemie
05 Faculty of Science > Departement Chemie > Former Organization Units Chemistry > Anorganische Chemie (Sigel)
UniBasel Contributors:Sigel, Astrid and Sigel, Helmut
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Taylor & Francis
ISSN:0095-8972
e-ISSN:1029-0389
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
Last Modified:08 Jul 2019 13:34
Deposited On:08 Jul 2019 13:34

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