The Zn(II)-1,4,7-Trimethyl-1,4,7-Triazacyclononane Complex: A Monometallic Catalyst Active in Two Protonation States
In this paper, the unusual reactivity of the complex Zn(II)-1,4,7-trimethyl-1, 4,7-triazacyclononane (2) in the transesterification of the RNA-model substrate, HPNP (3), is reported. The dependence of the reactivity (k2) with pH does not follow the characteristic bell-shape profile typical of comple...
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| Format: | Article |
| Language: | English |
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Frontiers Media S.A.
2019-07-01
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| Series: | Frontiers in Chemistry |
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| Online Access: | https://www.frontiersin.org/article/10.3389/fchem.2019.00469/full |
| _version_ | 1818879531139727360 |
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| author | Marta Diez-Castellnou Giovanni Salassa Fabrizio Mancin Paolo Scrimin |
| author_facet | Marta Diez-Castellnou Giovanni Salassa Fabrizio Mancin Paolo Scrimin |
| author_sort | Marta Diez-Castellnou |
| collection | DOAJ |
| description | In this paper, the unusual reactivity of the complex Zn(II)-1,4,7-trimethyl-1, 4,7-triazacyclononane (2) in the transesterification of the RNA-model substrate, HPNP (3), is reported. The dependence of the reactivity (k2) with pH does not follow the characteristic bell-shape profile typical of complexes with penta-coordinated metal centers. By the contrary, two reactive species, featuring different deprotonation states, are present, with the tri-aqua complex being more reactive than the mono-hydroxy-diaqua one. Apparently, such a difference arises from the total complex charge which plays an important role in the stability of the transition state/s of the reactions. Relevant insight on the reaction mechanism were hence obtained. |
| first_indexed | 2024-12-19T14:31:33Z |
| format | Article |
| id | doaj.art-53758412a7714443a7ed908a15eaa3a9 |
| institution | Directory Open Access Journal |
| issn | 2296-2646 |
| language | English |
| last_indexed | 2024-12-19T14:31:33Z |
| publishDate | 2019-07-01 |
| publisher | Frontiers Media S.A. |
| record_format | Article |
| series | Frontiers in Chemistry |
| spelling | doaj.art-53758412a7714443a7ed908a15eaa3a92022-12-21T20:17:25ZengFrontiers Media S.A.Frontiers in Chemistry2296-26462019-07-01710.3389/fchem.2019.00469464633The Zn(II)-1,4,7-Trimethyl-1,4,7-Triazacyclononane Complex: A Monometallic Catalyst Active in Two Protonation StatesMarta Diez-Castellnou0Giovanni Salassa1Fabrizio Mancin2Paolo Scrimin3EaStCHEM School of Chemistry, University of St Andrews, St. Andrews, United KingdomDépartement de Chimie Physique, Université de Genève, Genève, SwitzerlandDipartimento di Scienze Chimiche, Università di Padova, Padova, ItalyDipartimento di Scienze Chimiche, Università di Padova, Padova, ItalyIn this paper, the unusual reactivity of the complex Zn(II)-1,4,7-trimethyl-1, 4,7-triazacyclononane (2) in the transesterification of the RNA-model substrate, HPNP (3), is reported. The dependence of the reactivity (k2) with pH does not follow the characteristic bell-shape profile typical of complexes with penta-coordinated metal centers. By the contrary, two reactive species, featuring different deprotonation states, are present, with the tri-aqua complex being more reactive than the mono-hydroxy-diaqua one. Apparently, such a difference arises from the total complex charge which plays an important role in the stability of the transition state/s of the reactions. Relevant insight on the reaction mechanism were hence obtained.https://www.frontiersin.org/article/10.3389/fchem.2019.00469/fullRNAmonometallic Zn(II)-complexesazacrownphosphate cleavagephosphoesterase modelskinetics |
| spellingShingle | Marta Diez-Castellnou Giovanni Salassa Fabrizio Mancin Paolo Scrimin The Zn(II)-1,4,7-Trimethyl-1,4,7-Triazacyclononane Complex: A Monometallic Catalyst Active in Two Protonation States Frontiers in Chemistry RNA monometallic Zn(II)-complexes azacrown phosphate cleavage phosphoesterase models kinetics |
| title | The Zn(II)-1,4,7-Trimethyl-1,4,7-Triazacyclononane Complex: A Monometallic Catalyst Active in Two Protonation States |
| title_full | The Zn(II)-1,4,7-Trimethyl-1,4,7-Triazacyclononane Complex: A Monometallic Catalyst Active in Two Protonation States |
| title_fullStr | The Zn(II)-1,4,7-Trimethyl-1,4,7-Triazacyclononane Complex: A Monometallic Catalyst Active in Two Protonation States |
| title_full_unstemmed | The Zn(II)-1,4,7-Trimethyl-1,4,7-Triazacyclononane Complex: A Monometallic Catalyst Active in Two Protonation States |
| title_short | The Zn(II)-1,4,7-Trimethyl-1,4,7-Triazacyclononane Complex: A Monometallic Catalyst Active in Two Protonation States |
| title_sort | zn ii 1 4 7 trimethyl 1 4 7 triazacyclononane complex a monometallic catalyst active in two protonation states |
| topic | RNA monometallic Zn(II)-complexes azacrown phosphate cleavage phosphoesterase models kinetics |
| url | https://www.frontiersin.org/article/10.3389/fchem.2019.00469/full |
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