Origin of Selectivity of a Triazinyl Ligand for Americium(III) over Neodymium(III)

David Dan; Cristian Celis-Barros; Frankie D. White; Joseph M. Sperling; Thomas E. Albrecht-Schmitt

doi:10.1002/chem.201806070

Origin of Selectivity of a Triazinyl Ligand for Americium(III) over Neodymium(III)

David Dan, Cristian Celis-Barros, Frankie D. White, Joseph M. Sperling, Thomas E. Albrecht-Schmitt

Research output: Contribution to journal › Article › peer-review

34 Scopus citations

Abstract

[M(EtBTP) ₃ ][BPh ₄ ] ₃ ⋅3 CH ₃ CN (M=Nd, Am; EtBTP=2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)pyridine) have been synthesized from reactions of MCl ₃ ⋅n H ₂ O with EtBTP in acetonitrile followed by anion metathesis. Structural analysis reveals that these compounds contain M ³⁺ cations bound by tridentate EtBTP ligands to create a tricapped trigonal prismatic geometry around the metal centers. Collection of high-resolution, single-crystal X-ray diffraction data also allowed reduction in bond lengths esd's, such that a slight contraction of Δ=0.0158(18) Å in the Am−N versus Nd−N bond lengths was observed, even though these cations ostensibly have matching ionic radii. Theoretical evaluation revealed enhanced metal–ligand bonding through back donation in the [Am(EtBTP) ₃ ] ³⁺ complex that is absent in [Nd(EtBTP) ₃ ] ³⁺ .

Original language	English
Pages (from-to)	3248-3252
Number of pages	5
Journal	Chemistry - A European Journal
Volume	25
Issue number	13
DOIs	https://doi.org/10.1002/chem.201806070
State	Published - Mar 1 2019
Externally published	Yes

Funding

This research was supported by the Center for Actinide Science and Technology (CAST), an Energy Frontier Research Center (EFRC) funded by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under award number DE-SC0016568.

Funders	Funder number
Center for Actinide Science and Technology
Energy Frontier Research Center
US Department of Energy
U.S. Department of Energy
Office of Science
Basic Energy Sciences	DE-SC0016568

Keywords

actinides
americium complexation
coordination chemistry
lanthanides
neodymium complexation

Access to Document

10.1002/chem.201806070

Cite this

@article{aba6445179a04edea1a99133d0501aa0,

title = "Origin of Selectivity of a Triazinyl Ligand for Americium(III) over Neodymium(III)",

abstract = " [M(EtBTP) 3 ][BPh 4 ] 3 ⋅3 CH 3 CN (M=Nd, Am; EtBTP=2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)pyridine) have been synthesized from reactions of MCl 3 ⋅n H 2 O with EtBTP in acetonitrile followed by anion metathesis. Structural analysis reveals that these compounds contain M 3+ cations bound by tridentate EtBTP ligands to create a tricapped trigonal prismatic geometry around the metal centers. Collection of high-resolution, single-crystal X-ray diffraction data also allowed reduction in bond lengths esd's, such that a slight contraction of Δ=0.0158(18) {\AA} in the Am−N versus Nd−N bond lengths was observed, even though these cations ostensibly have matching ionic radii. Theoretical evaluation revealed enhanced metal–ligand bonding through back donation in the [Am(EtBTP) 3 ] 3+ complex that is absent in [Nd(EtBTP) 3 ] 3+ .",

keywords = "actinides, americium complexation, coordination chemistry, lanthanides, neodymium complexation",

author = "David Dan and Cristian Celis-Barros and White, {Frankie D.} and Sperling, {Joseph M.} and Albrecht-Schmitt, {Thomas E.}",

note = "Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2019",

month = mar,

day = "1",

doi = "10.1002/chem.201806070",

language = "English",

volume = "25",

pages = "3248--3252",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "wiley",

number = "13",

}

TY - JOUR

T1 - Origin of Selectivity of a Triazinyl Ligand for Americium(III) over Neodymium(III)

AU - Dan, David

AU - Celis-Barros, Cristian

AU - White, Frankie D.

AU - Sperling, Joseph M.

AU - Albrecht-Schmitt, Thomas E.

PY - 2019/3/1

Y1 - 2019/3/1

N2 - [M(EtBTP) 3 ][BPh 4 ] 3 ⋅3 CH 3 CN (M=Nd, Am; EtBTP=2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)pyridine) have been synthesized from reactions of MCl 3 ⋅n H 2 O with EtBTP in acetonitrile followed by anion metathesis. Structural analysis reveals that these compounds contain M 3+ cations bound by tridentate EtBTP ligands to create a tricapped trigonal prismatic geometry around the metal centers. Collection of high-resolution, single-crystal X-ray diffraction data also allowed reduction in bond lengths esd's, such that a slight contraction of Δ=0.0158(18) Å in the Am−N versus Nd−N bond lengths was observed, even though these cations ostensibly have matching ionic radii. Theoretical evaluation revealed enhanced metal–ligand bonding through back donation in the [Am(EtBTP) 3 ] 3+ complex that is absent in [Nd(EtBTP) 3 ] 3+ .

AB - [M(EtBTP) 3 ][BPh 4 ] 3 ⋅3 CH 3 CN (M=Nd, Am; EtBTP=2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)pyridine) have been synthesized from reactions of MCl 3 ⋅n H 2 O with EtBTP in acetonitrile followed by anion metathesis. Structural analysis reveals that these compounds contain M 3+ cations bound by tridentate EtBTP ligands to create a tricapped trigonal prismatic geometry around the metal centers. Collection of high-resolution, single-crystal X-ray diffraction data also allowed reduction in bond lengths esd's, such that a slight contraction of Δ=0.0158(18) Å in the Am−N versus Nd−N bond lengths was observed, even though these cations ostensibly have matching ionic radii. Theoretical evaluation revealed enhanced metal–ligand bonding through back donation in the [Am(EtBTP) 3 ] 3+ complex that is absent in [Nd(EtBTP) 3 ] 3+ .

KW - actinides

KW - americium complexation

KW - coordination chemistry

KW - lanthanides

KW - neodymium complexation

UR - http://www.scopus.com/inward/record.url?scp=85061028012&partnerID=8YFLogxK

U2 - 10.1002/chem.201806070

DO - 10.1002/chem.201806070

M3 - Article

C2 - 30716170

AN - SCOPUS:85061028012

SN - 0947-6539

VL - 25

SP - 3248

EP - 3252

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 13

ER -

Origin of Selectivity of a Triazinyl Ligand for Americium(III) over Neodymium(III)

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Cite this