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Prodigiosin Analogue Designed for Metal Coordination: Stable Zinc and Copper Pyrrolyldipyrrins
[Image: see text] The pyrrolyldipyrrin motif is found in several naturally occurring prodigiosin pigments. The potential roles of the interactions of prodigiosins with transition metals and the properties of metal-bound pyrrolyldipyrrins, however, have been difficult to assess because of the very li...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2014
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4106694/ https://www.ncbi.nlm.nih.gov/pubmed/25008284 http://dx.doi.org/10.1021/ic5008439 |
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author | Chang, Tsuhen M. Sinharay, Sanhita Astashkin, Andrei V. Tomat, Elisa |
author_facet | Chang, Tsuhen M. Sinharay, Sanhita Astashkin, Andrei V. Tomat, Elisa |
author_sort | Chang, Tsuhen M. |
collection | PubMed |
description | [Image: see text] The pyrrolyldipyrrin motif is found in several naturally occurring prodigiosin pigments. The potential roles of the interactions of prodigiosins with transition metals and the properties of metal-bound pyrrolyldipyrrins, however, have been difficult to assess because of the very limited number of well-characterized stable complexes. Here, we show that the introduction of a meso-aryl substituent and an ethyl ester group during the sequential assembly of the three heterocycles affords a pyrrolyldipyrrin of enhanced coordinating abilities when compared to that of natural prodigiosins. UV–visible absorption studies indicate that this ligand promptly binds Zn(II) ions with 2:1 ligand-to-metal stoichiometry and Cu(II) ions with 1:1 stoichiometry. Notably, no addition of base is required for the formation of the resulting stable complexes. The crystal structures reveal that whereas the tetrahedral zinc center engages two nitrogen donors on each ligand, the pseudosquare planar copper complex features coordination of all three pyrrolic nitrogen atoms and employs the ester group as a neutral ligand. This first example of coordination of a redox-active transition metal within a fully conjugated pyrrolyldipyrrin framework was investigated spectroscopically by electron paramagnetic resonance to show that the 1:1 metal-to-ligand ratio found in the crystal structure is also maintained in solution. |
format | Online Article Text |
id | pubmed-4106694 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2014 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-41066942015-07-10 Prodigiosin Analogue Designed for Metal Coordination: Stable Zinc and Copper Pyrrolyldipyrrins Chang, Tsuhen M. Sinharay, Sanhita Astashkin, Andrei V. Tomat, Elisa Inorg Chem [Image: see text] The pyrrolyldipyrrin motif is found in several naturally occurring prodigiosin pigments. The potential roles of the interactions of prodigiosins with transition metals and the properties of metal-bound pyrrolyldipyrrins, however, have been difficult to assess because of the very limited number of well-characterized stable complexes. Here, we show that the introduction of a meso-aryl substituent and an ethyl ester group during the sequential assembly of the three heterocycles affords a pyrrolyldipyrrin of enhanced coordinating abilities when compared to that of natural prodigiosins. UV–visible absorption studies indicate that this ligand promptly binds Zn(II) ions with 2:1 ligand-to-metal stoichiometry and Cu(II) ions with 1:1 stoichiometry. Notably, no addition of base is required for the formation of the resulting stable complexes. The crystal structures reveal that whereas the tetrahedral zinc center engages two nitrogen donors on each ligand, the pseudosquare planar copper complex features coordination of all three pyrrolic nitrogen atoms and employs the ester group as a neutral ligand. This first example of coordination of a redox-active transition metal within a fully conjugated pyrrolyldipyrrin framework was investigated spectroscopically by electron paramagnetic resonance to show that the 1:1 metal-to-ligand ratio found in the crystal structure is also maintained in solution. American Chemical Society 2014-07-10 2014-07-21 /pmc/articles/PMC4106694/ /pubmed/25008284 http://dx.doi.org/10.1021/ic5008439 Text en Copyright © 2014 American Chemical Society Terms of Use (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) |
spellingShingle | Chang, Tsuhen M. Sinharay, Sanhita Astashkin, Andrei V. Tomat, Elisa Prodigiosin Analogue Designed for Metal Coordination: Stable Zinc and Copper Pyrrolyldipyrrins |
title | Prodigiosin Analogue Designed for Metal Coordination:
Stable Zinc and Copper Pyrrolyldipyrrins |
title_full | Prodigiosin Analogue Designed for Metal Coordination:
Stable Zinc and Copper Pyrrolyldipyrrins |
title_fullStr | Prodigiosin Analogue Designed for Metal Coordination:
Stable Zinc and Copper Pyrrolyldipyrrins |
title_full_unstemmed | Prodigiosin Analogue Designed for Metal Coordination:
Stable Zinc and Copper Pyrrolyldipyrrins |
title_short | Prodigiosin Analogue Designed for Metal Coordination:
Stable Zinc and Copper Pyrrolyldipyrrins |
title_sort | prodigiosin analogue designed for metal coordination:
stable zinc and copper pyrrolyldipyrrins |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4106694/ https://www.ncbi.nlm.nih.gov/pubmed/25008284 http://dx.doi.org/10.1021/ic5008439 |
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