Gas-Phase Complexes of Americium and Lanthanides with a Bis-triazinyl Pyridine: Reactivity and Bonding of Archetypes for F-Element Separations
Abstract
Bis-triazinyl pyridines (BTPs) exhibit solution selectivity for trivalent americium over lanthanides (Ln), the origins of which remain uncertain. Here in this paper, electrospray ionization was used to generate gas-phase complexes [ML3]3+, where M = La, Lu, or Am and L is EtBTP 2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)-pyridine. Collision-induced dissociation (CID) of [ML3]3+ in the presence of H2O yielded a protonated ligand [L(H)]+ and hydroxide [ML2(OH)]2+ or hydrate [ML(L–H)(H2O)]2+, where (L–H)- is a deprotonated ligand. Although solution affinities indicate stronger binding of BTPs toward Am3+ versus Ln3+, the observed CID process is contrastingly more facile for M = Am versus Ln. To understand the disparity, density functional theory was employed to compute potential energy surfaces for two possible CID processes, for M = La and Am. In accordance with the CID results, both the rate determining transition state barrier and the net energy are lower for [AmL3]3+ versus [LaL3]3+ and for both product isomers, [ML2(OH)]2+ and [ML(L–H)(H2O)]2+. More facile removal of a ligand from [AmL3]3+ by CID does not necessarily contradict stronger Am3+–L binding, as inferred from solution behavior. In particular, the formation of new bonds in the products can distort kinetics and thermodynamics expected for simple bond cleavage reactions. In addition to correctly predictingmore »
- Authors:
-
[1];
[2];
[1]
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- State Univ. of New York (SUNY), Buffalo, NY (United States)
- Florida State Univ., Tallahassee, FL (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Actinide Science & Technology (CAST); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1631653
- Grant/Contract Number:
- AC02-05CH11231; SC0016568
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 124; Journal Issue: 15; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Jian, Tian, Yu, Xiaojuan, Dan, David, Albrecht-Schmitt, Thomas E., Autschbach, Jochen, and Gibson, John K. Gas-Phase Complexes of Americium and Lanthanides with a Bis-triazinyl Pyridine: Reactivity and Bonding of Archetypes for F-Element Separations. United States: N. p., 2020.
Web. doi:10.1021/acs.jpca.0c00675.
Jian, Tian, Yu, Xiaojuan, Dan, David, Albrecht-Schmitt, Thomas E., Autschbach, Jochen, & Gibson, John K. Gas-Phase Complexes of Americium and Lanthanides with a Bis-triazinyl Pyridine: Reactivity and Bonding of Archetypes for F-Element Separations. United States. https://doi.org/10.1021/acs.jpca.0c00675
Jian, Tian, Yu, Xiaojuan, Dan, David, Albrecht-Schmitt, Thomas E., Autschbach, Jochen, and Gibson, John K. Tue .
"Gas-Phase Complexes of Americium and Lanthanides with a Bis-triazinyl Pyridine: Reactivity and Bonding of Archetypes for F-Element Separations". United States. https://doi.org/10.1021/acs.jpca.0c00675. https://www.osti.gov/servlets/purl/1631653.
@article{osti_1631653,
title = {Gas-Phase Complexes of Americium and Lanthanides with a Bis-triazinyl Pyridine: Reactivity and Bonding of Archetypes for F-Element Separations},
author = {Jian, Tian and Yu, Xiaojuan and Dan, David and Albrecht-Schmitt, Thomas E. and Autschbach, Jochen and Gibson, John K.},
abstractNote = {Bis-triazinyl pyridines (BTPs) exhibit solution selectivity for trivalent americium over lanthanides (Ln), the origins of which remain uncertain. Here in this paper, electrospray ionization was used to generate gas-phase complexes [ML3]3+, where M = La, Lu, or Am and L is EtBTP 2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)-pyridine. Collision-induced dissociation (CID) of [ML3]3+ in the presence of H2O yielded a protonated ligand [L(H)]+ and hydroxide [ML2(OH)]2+ or hydrate [ML(L–H)(H2O)]2+, where (L–H)- is a deprotonated ligand. Although solution affinities indicate stronger binding of BTPs toward Am3+ versus Ln3+, the observed CID process is contrastingly more facile for M = Am versus Ln. To understand the disparity, density functional theory was employed to compute potential energy surfaces for two possible CID processes, for M = La and Am. In accordance with the CID results, both the rate determining transition state barrier and the net energy are lower for [AmL3]3+ versus [LaL3]3+ and for both product isomers, [ML2(OH)]2+ and [ML(L–H)(H2O)]2+. More facile removal of a ligand from [AmL3]3+ by CID does not necessarily contradict stronger Am3+–L binding, as inferred from solution behavior. In particular, the formation of new bonds in the products can distort kinetics and thermodynamics expected for simple bond cleavage reactions. In addition to correctly predicting the seemingly anomalous CID behavior, the computational results indicate greater participation of Am 5f versus La 4f orbitals in metal–ligand bonding.},
doi = {10.1021/acs.jpca.0c00675},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 15,
volume = 124,
place = {United States},
year = {Tue Mar 24 00:00:00 EDT 2020},
month = {Tue Mar 24 00:00:00 EDT 2020}
}
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