Differentiating between trivalent lanthanides and actinides

Matthew J. Polinski, Daniel J. Grant, Shuao Wang, Evgeny V. Alekseev, Justin N. Cross, Eric Villa, Wulf Depmeier, Laura Gagliardi, Thomas E. Albrecht-Schmitt

Research output: Contribution to journalArticle

71 Citations (Scopus)

Abstract

The reactions of LnCl 3 with molten boric acid result in the formation of Ln[B 4O 6(OH) 2Cl] (Ln = La-Nd), Ln 4[B 18O 25(OH) 13Cl 3] (Ln = Sm, Eu), or Ln[B 6O 9(OH) 3] (Ln = Y, Eu-Lu). The reactions of AnCl 3 (An = Pu, Am, Cm) with molten boric acid under the same conditions yield Pu[B 4O 6(OH) 2Cl] and Pu 2[B 13O 19(OH) 5Cl 2(H 2O) 3], Am[B 9O 13(OH) 4]•H 2O, or Cm 2[B 14O 20(OH) 7(H 2O) 2Cl]. These compounds possess three-dimensional network structures where rare earth borate layers are joined together by BO 3 and/or BO 4 groups. There is a shift from 10-coordinate Ln 3+ and An 3+ cations with capped triangular cupola geometries for the early members of both series to 9-coordinate hula-hoop geometries for the later elements. Cm 3+ is anomalous in that it contains both 9- and 10-coordinate metal ions. Despite these materials being synthesized under identical conditions, the two series do not parallel one another. Electronic structure calculations with multireference, CASSCF, and density functional theory (DFT) methods reveal the An 5f orbitals to be localized and predominately uninvolved in bonding. For the Pu(III) borates, a Pu 6p orbital is observed with delocalized electron density on basal oxygen atoms contrasting the Am(III) and Cm(III) borates, where a basal O 2p orbital delocalizes to the An 6d orbital. The electronic structure of the Ce(III) borate is similar to the Pu(III) complexes in that the Ce 4f orbital is localized and noninteracting, but the Ce 5p orbital shows no interaction with the coordinating ligands. Natural bond orbital and natural population analyses at the DFT level illustrate distinctive larger Pu 5f atomic occupancy relative to Am and Cm 5f, as well as unique involvement and occupancy of the An 6d orbitals.

Original languageEnglish
Pages (from-to)10682-10692
Number of pages11
JournalJournal of the American Chemical Society
Volume134
Issue number25
DOIs
StatePublished - Jun 27 2012
Externally publishedYes

Fingerprint

Actinoid Series Elements
Lanthanoid Series Elements
Borates
Actinides
Rare earth elements
Boric acid
Electronic structure
Density functional theory
Molten materials
Geometry
Rare earths
Carrier concentration
Metal ions
Cations
Positive ions
Metals
Ligands
Electrons
Ions
Oxygen

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Polinski, M. J., Grant, D. J., Wang, S., Alekseev, E. V., Cross, J. N., Villa, E., ... Albrecht-Schmitt, T. E. (2012). Differentiating between trivalent lanthanides and actinides. Journal of the American Chemical Society, 134(25), 10682-10692. https://doi.org/10.1021/ja303804r

Differentiating between trivalent lanthanides and actinides. / Polinski, Matthew J.; Grant, Daniel J.; Wang, Shuao; Alekseev, Evgeny V.; Cross, Justin N.; Villa, Eric; Depmeier, Wulf; Gagliardi, Laura; Albrecht-Schmitt, Thomas E.

In: Journal of the American Chemical Society, Vol. 134, No. 25, 27.06.2012, p. 10682-10692.

Research output: Contribution to journalArticle

Polinski, MJ, Grant, DJ, Wang, S, Alekseev, EV, Cross, JN, Villa, E, Depmeier, W, Gagliardi, L & Albrecht-Schmitt, TE 2012, 'Differentiating between trivalent lanthanides and actinides', Journal of the American Chemical Society, vol. 134, no. 25, pp. 10682-10692. https://doi.org/10.1021/ja303804r
Polinski MJ, Grant DJ, Wang S, Alekseev EV, Cross JN, Villa E et al. Differentiating between trivalent lanthanides and actinides. Journal of the American Chemical Society. 2012 Jun 27;134(25):10682-10692. https://doi.org/10.1021/ja303804r
Polinski, Matthew J. ; Grant, Daniel J. ; Wang, Shuao ; Alekseev, Evgeny V. ; Cross, Justin N. ; Villa, Eric ; Depmeier, Wulf ; Gagliardi, Laura ; Albrecht-Schmitt, Thomas E. / Differentiating between trivalent lanthanides and actinides. In: Journal of the American Chemical Society. 2012 ; Vol. 134, No. 25. pp. 10682-10692.
@article{aae888a089b24083ad045e0606b7c3e9,
title = "Differentiating between trivalent lanthanides and actinides",
abstract = "The reactions of LnCl 3 with molten boric acid result in the formation of Ln[B 4O 6(OH) 2Cl] (Ln = La-Nd), Ln 4[B 18O 25(OH) 13Cl 3] (Ln = Sm, Eu), or Ln[B 6O 9(OH) 3] (Ln = Y, Eu-Lu). The reactions of AnCl 3 (An = Pu, Am, Cm) with molten boric acid under the same conditions yield Pu[B 4O 6(OH) 2Cl] and Pu 2[B 13O 19(OH) 5Cl 2(H 2O) 3], Am[B 9O 13(OH) 4]•H 2O, or Cm 2[B 14O 20(OH) 7(H 2O) 2Cl]. These compounds possess three-dimensional network structures where rare earth borate layers are joined together by BO 3 and/or BO 4 groups. There is a shift from 10-coordinate Ln 3+ and An 3+ cations with capped triangular cupola geometries for the early members of both series to 9-coordinate hula-hoop geometries for the later elements. Cm 3+ is anomalous in that it contains both 9- and 10-coordinate metal ions. Despite these materials being synthesized under identical conditions, the two series do not parallel one another. Electronic structure calculations with multireference, CASSCF, and density functional theory (DFT) methods reveal the An 5f orbitals to be localized and predominately uninvolved in bonding. For the Pu(III) borates, a Pu 6p orbital is observed with delocalized electron density on basal oxygen atoms contrasting the Am(III) and Cm(III) borates, where a basal O 2p orbital delocalizes to the An 6d orbital. The electronic structure of the Ce(III) borate is similar to the Pu(III) complexes in that the Ce 4f orbital is localized and noninteracting, but the Ce 5p orbital shows no interaction with the coordinating ligands. Natural bond orbital and natural population analyses at the DFT level illustrate distinctive larger Pu 5f atomic occupancy relative to Am and Cm 5f, as well as unique involvement and occupancy of the An 6d orbitals.",
author = "Polinski, {Matthew J.} and Grant, {Daniel J.} and Shuao Wang and Alekseev, {Evgeny V.} and Cross, {Justin N.} and Eric Villa and Wulf Depmeier and Laura Gagliardi and Albrecht-Schmitt, {Thomas E.}",
year = "2012",
month = "6",
day = "27",
doi = "10.1021/ja303804r",
language = "English",
volume = "134",
pages = "10682--10692",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "25",

}

TY - JOUR

T1 - Differentiating between trivalent lanthanides and actinides

AU - Polinski, Matthew J.

AU - Grant, Daniel J.

AU - Wang, Shuao

AU - Alekseev, Evgeny V.

AU - Cross, Justin N.

AU - Villa, Eric

AU - Depmeier, Wulf

AU - Gagliardi, Laura

AU - Albrecht-Schmitt, Thomas E.

PY - 2012/6/27

Y1 - 2012/6/27

N2 - The reactions of LnCl 3 with molten boric acid result in the formation of Ln[B 4O 6(OH) 2Cl] (Ln = La-Nd), Ln 4[B 18O 25(OH) 13Cl 3] (Ln = Sm, Eu), or Ln[B 6O 9(OH) 3] (Ln = Y, Eu-Lu). The reactions of AnCl 3 (An = Pu, Am, Cm) with molten boric acid under the same conditions yield Pu[B 4O 6(OH) 2Cl] and Pu 2[B 13O 19(OH) 5Cl 2(H 2O) 3], Am[B 9O 13(OH) 4]•H 2O, or Cm 2[B 14O 20(OH) 7(H 2O) 2Cl]. These compounds possess three-dimensional network structures where rare earth borate layers are joined together by BO 3 and/or BO 4 groups. There is a shift from 10-coordinate Ln 3+ and An 3+ cations with capped triangular cupola geometries for the early members of both series to 9-coordinate hula-hoop geometries for the later elements. Cm 3+ is anomalous in that it contains both 9- and 10-coordinate metal ions. Despite these materials being synthesized under identical conditions, the two series do not parallel one another. Electronic structure calculations with multireference, CASSCF, and density functional theory (DFT) methods reveal the An 5f orbitals to be localized and predominately uninvolved in bonding. For the Pu(III) borates, a Pu 6p orbital is observed with delocalized electron density on basal oxygen atoms contrasting the Am(III) and Cm(III) borates, where a basal O 2p orbital delocalizes to the An 6d orbital. The electronic structure of the Ce(III) borate is similar to the Pu(III) complexes in that the Ce 4f orbital is localized and noninteracting, but the Ce 5p orbital shows no interaction with the coordinating ligands. Natural bond orbital and natural population analyses at the DFT level illustrate distinctive larger Pu 5f atomic occupancy relative to Am and Cm 5f, as well as unique involvement and occupancy of the An 6d orbitals.

AB - The reactions of LnCl 3 with molten boric acid result in the formation of Ln[B 4O 6(OH) 2Cl] (Ln = La-Nd), Ln 4[B 18O 25(OH) 13Cl 3] (Ln = Sm, Eu), or Ln[B 6O 9(OH) 3] (Ln = Y, Eu-Lu). The reactions of AnCl 3 (An = Pu, Am, Cm) with molten boric acid under the same conditions yield Pu[B 4O 6(OH) 2Cl] and Pu 2[B 13O 19(OH) 5Cl 2(H 2O) 3], Am[B 9O 13(OH) 4]•H 2O, or Cm 2[B 14O 20(OH) 7(H 2O) 2Cl]. These compounds possess three-dimensional network structures where rare earth borate layers are joined together by BO 3 and/or BO 4 groups. There is a shift from 10-coordinate Ln 3+ and An 3+ cations with capped triangular cupola geometries for the early members of both series to 9-coordinate hula-hoop geometries for the later elements. Cm 3+ is anomalous in that it contains both 9- and 10-coordinate metal ions. Despite these materials being synthesized under identical conditions, the two series do not parallel one another. Electronic structure calculations with multireference, CASSCF, and density functional theory (DFT) methods reveal the An 5f orbitals to be localized and predominately uninvolved in bonding. For the Pu(III) borates, a Pu 6p orbital is observed with delocalized electron density on basal oxygen atoms contrasting the Am(III) and Cm(III) borates, where a basal O 2p orbital delocalizes to the An 6d orbital. The electronic structure of the Ce(III) borate is similar to the Pu(III) complexes in that the Ce 4f orbital is localized and noninteracting, but the Ce 5p orbital shows no interaction with the coordinating ligands. Natural bond orbital and natural population analyses at the DFT level illustrate distinctive larger Pu 5f atomic occupancy relative to Am and Cm 5f, as well as unique involvement and occupancy of the An 6d orbitals.

UR - http://www.scopus.com/inward/record.url?scp=84863422453&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84863422453&partnerID=8YFLogxK

U2 - 10.1021/ja303804r

DO - 10.1021/ja303804r

M3 - Article

C2 - 22642795

AN - SCOPUS:84863422453

VL - 134

SP - 10682

EP - 10692

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 25

ER -