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 (k(2)) with pH does not follow the characteristic bell-shape profile typical of comp...

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Autores principales: Diez-Castellnou, Marta, Salassa, Giovanni, Mancin, Fabrizio, Scrimin, Paolo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Frontiers Media S.A. 2019
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6616306/
https://www.ncbi.nlm.nih.gov/pubmed/31334218
http://dx.doi.org/10.3389/fchem.2019.00469
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author Diez-Castellnou, Marta
Salassa, Giovanni
Mancin, Fabrizio
Scrimin, Paolo
author_facet Diez-Castellnou, Marta
Salassa, Giovanni
Mancin, Fabrizio
Scrimin, Paolo
author_sort Diez-Castellnou, Marta
collection PubMed
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 (k(2)) 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.
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spelling pubmed-66163062019-07-22 The Zn(II)-1,4,7-Trimethyl-1,4,7-Triazacyclononane Complex: A Monometallic Catalyst Active in Two Protonation States Diez-Castellnou, Marta Salassa, Giovanni Mancin, Fabrizio Scrimin, Paolo Front Chem Chemistry 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 (k(2)) 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. Frontiers Media S.A. 2019-07-03 /pmc/articles/PMC6616306/ /pubmed/31334218 http://dx.doi.org/10.3389/fchem.2019.00469 Text en Copyright © 2019 Diez-Castellnou, Salassa, Mancin and Scrimin. http://creativecommons.org/licenses/by/4.0/ This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.
spellingShingle Chemistry
Diez-Castellnou, Marta
Salassa, Giovanni
Mancin, Fabrizio
Scrimin, Paolo
The Zn(II)-1,4,7-Trimethyl-1,4,7-Triazacyclononane Complex: A Monometallic Catalyst Active in Two Protonation States
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 Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6616306/
https://www.ncbi.nlm.nih.gov/pubmed/31334218
http://dx.doi.org/10.3389/fchem.2019.00469
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