DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Bis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency

Abstract

Here, we report a new family of preorganized bislactam- 1,10-phenanthroline (BLPhen) complexants that possess both hard and soft donor atoms within a convergent cavity and show unprecedented extraction strength for the trivalent fblock metal ions. BLPhen ligands with saturated and unsaturated δ-lactam rings have notable differences in their affinity and selectivity for Am(III) over Eu(III), with the latter being the most selective mixed N,O-donor extractant of Am(III) reported to date. Saturated BLPhen was crystallized with five Ln(III) nitrates to form charge-neutral 1:1 complexes in the solid state. DFT calculations further elaborate on the variety of effects that dictate the performance of these preorganized compounds.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1];  [1];  [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE), Fuel Cycle Technologies (NE-5)
OSTI Identifier:
1356918
Grant/Contract Number:  
AC05-00OR22725; AC01-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 56; Journal Issue: 10; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Jansone-Popova, Santa, Ivanov, Alexander S., Bryantsev, Vyacheslav S., Sloop, Frederick V., Custelcean, Radu, Popovs, Ilja, Dekarske, Madeline M., and Moyer, Bruce A. Bis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency. United States: N. p., 2017. Web. doi:10.1021/acs.inorgchem.7b00555.
Jansone-Popova, Santa, Ivanov, Alexander S., Bryantsev, Vyacheslav S., Sloop, Frederick V., Custelcean, Radu, Popovs, Ilja, Dekarske, Madeline M., & Moyer, Bruce A. Bis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency. United States. https://doi.org/10.1021/acs.inorgchem.7b00555
Jansone-Popova, Santa, Ivanov, Alexander S., Bryantsev, Vyacheslav S., Sloop, Frederick V., Custelcean, Radu, Popovs, Ilja, Dekarske, Madeline M., and Moyer, Bruce A. Thu . "Bis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency". United States. https://doi.org/10.1021/acs.inorgchem.7b00555. https://www.osti.gov/servlets/purl/1356918.
@article{osti_1356918,
title = {Bis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency},
author = {Jansone-Popova, Santa and Ivanov, Alexander S. and Bryantsev, Vyacheslav S. and Sloop, Frederick V. and Custelcean, Radu and Popovs, Ilja and Dekarske, Madeline M. and Moyer, Bruce A.},
abstractNote = {Here, we report a new family of preorganized bislactam- 1,10-phenanthroline (BLPhen) complexants that possess both hard and soft donor atoms within a convergent cavity and show unprecedented extraction strength for the trivalent fblock metal ions. BLPhen ligands with saturated and unsaturated δ-lactam rings have notable differences in their affinity and selectivity for Am(III) over Eu(III), with the latter being the most selective mixed N,O-donor extractant of Am(III) reported to date. Saturated BLPhen was crystallized with five Ln(III) nitrates to form charge-neutral 1:1 complexes in the solid state. DFT calculations further elaborate on the variety of effects that dictate the performance of these preorganized compounds.},
doi = {10.1021/acs.inorgchem.7b00555},
journal = {Inorganic Chemistry},
number = 10,
volume = 56,
place = {United States},
year = {Thu May 04 00:00:00 EDT 2017},
month = {Thu May 04 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 40 works
Citation information provided by
Web of Science

Figures / Tables:

Scheme 1 Scheme 1: Structures of Soft N-Donor Ligands, BTBP and BTPhen, and Mixed N,O-Donor Ligands, BAPhen and BLPhen, in Their Preferred Conformationsa

Save / Share:

Works referenced in this record:

Separation of actinides from spent nuclear fuel: A review
journal, November 2016


Highly Efficient Separation of Actinides from Lanthanides by a Phenanthroline-Derived Bis-triazine Ligand
journal, August 2011

  • Lewis, Frank W.; Harwood, Laurence M.; Hudson, Michael J.
  • Journal of the American Chemical Society, Vol. 133, Issue 33
  • DOI: 10.1021/ja203378m

Utilizing electronic effects in the modulation of BTPhen ligands with respect to the partitioning of minor actinides from lanthanides
journal, January 2013

  • Afsar, Ashfaq; Laventine, Dominic M.; Harwood, Laurence M.
  • Chemical Communications, Vol. 49, Issue 76
  • DOI: 10.1039/c3cc45126g

Probing the difference in covalence by enthalpy measurements: a new heterocyclic N-donor ligand for actinide/lanthanide separation
journal, January 2015

  • Yang, Yanqiu; Liu, Jun; Yang, Liang
  • Dalton Transactions, Vol. 44, Issue 19
  • DOI: 10.1039/C5DT00679A

Complexation and Extraction of Trivalent Actinides and Lanthanides by Triazinylpyridine N -Donor Ligands
journal, October 2012

  • Panak, Petra J.; Geist, Andreas
  • Chemical Reviews, Vol. 113, Issue 2
  • DOI: 10.1021/cr3003399

Lanthanide Speciation in Potential SANEX and GANEX Actinide/Lanthanide Separations Using Tetra-N-Donor Extractants
journal, June 2012

  • Whittaker, Daniel M.; Griffiths, Tamara L.; Helliwell, Madeleine
  • Inorganic Chemistry, Vol. 52, Issue 7
  • DOI: 10.1021/ic301599y

Complexation and Separation of Lanthanides(III) and Actinides(III) by Heterocyclic N-Donors in Solutions
journal, October 2008


Use of Soft Heterocyclic N-Donor Ligands To Separate Actinides and Lanthanides
journal, June 2012

  • Hudson, Michael J.; Harwood, Laurence M.; Laventine, Dominic M.
  • Inorganic Chemistry, Vol. 52, Issue 7
  • DOI: 10.1021/ic3008848

Theoretical prediction of Am( iii )/Eu( iii ) selectivity to aid the design of actinide-lanthanide separation agents
journal, January 2015

  • Bryantsev, Vyacheslav S.; Hay, Benjamin P.
  • Dalton Transactions, Vol. 44, Issue 17
  • DOI: 10.1039/C4DT03275F

Highly Practical and Simple Ligand for Separation of Am(III) and Eu(III) from Highly Acidic Media
journal, January 2016

  • Suzuki, Hideya; Tsubata, Yasuhiro; Kurosawa, Tatsuya
  • Analytical Sciences, Vol. 32, Issue 4
  • DOI: 10.2116/analsci.32.477

New systems based on 2,2’-dipyridyl-6,6’-dicarboxylic acid diamides for Am–Eu separation
journal, November 2008

  • Alyapyshev, Mikhail Yu.; Babain, Vasily A.; Borisova, Nataliya E.
  • Mendeleev Communications, Vol. 18, Issue 6
  • DOI: 10.1016/j.mencom.2008.11.018

2,2′-Dipyridyl-6,6′-dicarboxylic acid diamides: Synthesis, complexation and extraction properties
journal, May 2010


The pyridyl group in ligand design for selective metal ion complexation and sensing
journal, January 2013


Deliberate Design of Ligand Architecture Yields Dramatic Enhancement of Metal Ion Affinity
journal, May 2002

  • Lumetta, Gregg J.; Rapko, Brian M.; Garza, Priscilla A.
  • Journal of the American Chemical Society, Vol. 124, Issue 20
  • DOI: 10.1021/ja025854t

Preorganization of diglycolamides on the calix[4]arene platform and its effect on the extraction of Am(III)/Eu(III)
journal, September 2012


2,9-Dicarbonyl-1,10-phenanthroline derivatives with an unprecedented Am(iii)/Eu(iii) selectivity under highly acidic conditions
journal, January 2013

  • Galletta, Michele; Scaravaggi, Stefano; Macerata, Elena
  • Dalton Transactions, Vol. 42, Issue 48
  • DOI: 10.1039/c3dt52104d

Excellent Selectivity for Actinides with a Tetradentate 2,9-Diamide-1,10-Phenanthroline Ligand in Highly Acidic Solution: A Hard–Soft Donor Combined Strategy
journal, January 2014

  • Xiao, Cheng-Liang; Wang, Cong-Zhi; Yuan, Li-Yong
  • Inorganic Chemistry, Vol. 53, Issue 3
  • DOI: 10.1021/ic402784c

Actinide selectivity of 1,10-phenanthroline-2,9-dicarboxamide and its derivatives: a theoretical prediction followed by experimental validation
journal, January 2015

  • Manna, Debashree; Mula, Soumyaditya; Bhattacharyya, Arunasis
  • Dalton Transactions, Vol. 44, Issue 3
  • DOI: 10.1039/C4DT02402H

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Energy-adjusted pseudopotentials for the rare earth elements
journal, January 1989

  • Dolg, M.; Stoll, H.; Savin, A.
  • Theoretica Chimica Acta, Vol. 75, Issue 3
  • DOI: 10.1007/BF00528565

Valence basis sets for relativistic energy-consistent small-core lanthanide pseudopotentials
journal, October 2001

  • Cao, Xiaoyan; Dolg, Michael
  • The Journal of Chemical Physics, Vol. 115, Issue 16
  • DOI: 10.1063/1.1406535

All-Electron Scalar Relativistic Basis Sets for Third-Row Transition Metal Atoms
journal, May 2008

  • Pantazis, Dimitrios A.; Chen, Xian-Yang; Landis, Clark R.
  • Journal of Chemical Theory and Computation, Vol. 4, Issue 6
  • DOI: 10.1021/ct800047t

Contracted Gaussian basis sets for Douglas–Kroll–Hess calculations: Estimating scalar relativistic effects of some atomic and molecular properties
journal, February 2009

  • Jorge, F. E.; Canal Neto, A.; Camiletti, G. G.
  • The Journal of Chemical Physics, Vol. 130, Issue 6
  • DOI: 10.1063/1.3072360

Quantum Mechanical Continuum Solvation Models
journal, August 2005

  • Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
  • Chemical Reviews, Vol. 105, Issue 8
  • DOI: 10.1021/cr9904009

Natural hybrid orbitals
journal, September 1980

  • Foster, J. P.; Weinhold, F.
  • Journal of the American Chemical Society, Vol. 102, Issue 24
  • DOI: 10.1021/ja00544a007

Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint
journal, September 1988

  • Reed, Alan E.; Curtiss, Larry A.; Weinhold, Frank
  • Chemical Reviews, Vol. 88, Issue 6
  • DOI: 10.1021/cr00088a005

Rhodium(III)-Catalyzed Isoquinolone Synthesis: The N−O Bond as a Handle for C−N Bond Formation and Catalyst Turnover
journal, April 2010

  • Guimond, Nicolas; Gouliaras, Christina; Fagnou, Keith
  • Journal of the American Chemical Society, Vol. 132, Issue 20
  • DOI: 10.1021/ja102571b

Rhodium(III)-Catalyzed Heterocycle Synthesis Using an Internal Oxidant: Improved Reactivity and Mechanistic Studies
journal, April 2011

  • Guimond, Nicolas; Gorelsky, Serge I.; Fagnou, Keith
  • Journal of the American Chemical Society, Vol. 133, Issue 16
  • DOI: 10.1021/ja201143v

Energies and alkylations of tautomeric heterocyclic compounds: old problems - new answers
journal, May 1977


Works referencing / citing this record:

Efficient Separation of Light Lanthanides(III) by Using Bis‐Lactam Phenanthroline Ligands
journal, March 2019

  • Healy, Mary R.; Ivanov, Alexander S.; Karslyan, Yana
  • Chemistry – A European Journal, Vol. 25, Issue 25
  • DOI: 10.1002/chem.201806443

The impact of alicyclic substituents on the extraction ability of new family of 1,10-phenanthroline-2,9-diamides
journal, January 2020

  • Lemport, Pavel S.; Matveev, Petr I.; Yatsenko, Alexander V.
  • RSC Advances, Vol. 10, Issue 44
  • DOI: 10.1039/d0ra05182a

Sequestration of trivalent americium and lanthanide nitrates with bis-lactam-1,10-phenanthroline ligand in a hydrocarbon solvent
journal, January 2019

  • Karslyan, Yana; Sloop, Frederick V.; Delmau, Laetitia H.
  • RSC Advances, Vol. 9, Issue 46
  • DOI: 10.1039/c9ra06115k