Examination of Structure and Bonding in 10-Coordinate Europium and Americium Terpyridyl Complexes

Frankie D. White; Alyssa N. Gaiser; Evan J. Warzecha; Joseph M. Sperling; Cristian Celis-Barros; Sahan R. Salpage; Yan Zhou; Tristan Dilbeck; Andrew J. Bretton; David S. Meeker; Kenneth G. Hanson; Thomas E. Albrecht-Schmitt

doi:10.1021/acs.inorgchem.8b02085

Examination of Structure and Bonding in 10-Coordinate Europium and Americium Terpyridyl Complexes

Frankie D. White, Alyssa N. Gaiser, Evan J. Warzecha, Joseph M. Sperling, Cristian Celis-Barros, Sahan R. Salpage, Yan Zhou, Tristan Dilbeck, Andrew J. Bretton, David S. Meeker, Kenneth G. Hanson, Thomas E. Albrecht-Schmitt

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

23 Scopus citations

Abstract

M(TpyNO₂)(NO₃)₃(H₂O)·THF (M = La, Nd, Sm, Eu, Tb, Am; TpyNO₂ = 4′-nitrophenyl terpyridyl) have been prepared from the reaction of M(NO₃)₃·nH₂O with TpyNO₂ in THF. Structural analysis shows that the metal centers are 10-coordinate, providing the first example of Am^III with this coordination number. Further spectroscopic and theoretical evaluation of these complexes reveals utilization of the 5f orbitals in bonding in the Am^III complex. Comparison of Nd-L, Eu-L, and Am-L bond distances demonstrates that some caution should be taken in comparing Eu^III versus Am^III in extraction experiments.

Original language	English
Pages (from-to)	12969-12975
Number of pages	7
Journal	Inorganic Chemistry
Volume	57
Issue number	20
DOIs	https://doi.org/10.1021/acs.inorgchem.8b02085
State	Published - Oct 15 2018
Externally published	Yes

Funding

This work was supported by the Department of Energy, Heavy Elements Chemistry Program under Award Number DE-FG02-13ER16414. We would also like to thank Jason Johnson and Ashley Gray at Florida State University for their role in radiation work.

Funders	Funder number
U.S. Department of Energy	DE-FG02-13ER16414

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White, F. D., Gaiser, A. N., Warzecha, E. J., Sperling, J. M., Celis-Barros, C., Salpage, S. R., Zhou, Y., Dilbeck, T., Bretton, A. J., Meeker, D. S., Hanson, K. G., & Albrecht-Schmitt, T. E. (2018). Examination of Structure and Bonding in 10-Coordinate Europium and Americium Terpyridyl Complexes. Inorganic Chemistry, 57(20), 12969-12975. https://doi.org/10.1021/acs.inorgchem.8b02085

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title = "Examination of Structure and Bonding in 10-Coordinate Europium and Americium Terpyridyl Complexes",

abstract = "M(TpyNO2)(NO3)3(H2O)·THF (M = La, Nd, Sm, Eu, Tb, Am; TpyNO2 = 4′-nitrophenyl terpyridyl) have been prepared from the reaction of M(NO3)3·nH2O with TpyNO2 in THF. Structural analysis shows that the metal centers are 10-coordinate, providing the first example of AmIII with this coordination number. Further spectroscopic and theoretical evaluation of these complexes reveals utilization of the 5f orbitals in bonding in the AmIII complex. Comparison of Nd-L, Eu-L, and Am-L bond distances demonstrates that some caution should be taken in comparing EuIII versus AmIII in extraction experiments.",

author = "White, {Frankie D.} and Gaiser, {Alyssa N.} and Warzecha, {Evan J.} and Sperling, {Joseph M.} and Cristian Celis-Barros and Salpage, {Sahan R.} and Yan Zhou and Tristan Dilbeck and Bretton, {Andrew J.} and Meeker, {David S.} and Hanson, {Kenneth G.} and Albrecht-Schmitt, {Thomas E.}",

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year = "2018",

month = oct,

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doi = "10.1021/acs.inorgchem.8b02085",

language = "English",

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T1 - Examination of Structure and Bonding in 10-Coordinate Europium and Americium Terpyridyl Complexes

AU - White, Frankie D.

AU - Gaiser, Alyssa N.

AU - Warzecha, Evan J.

AU - Sperling, Joseph M.

AU - Celis-Barros, Cristian

AU - Salpage, Sahan R.

AU - Zhou, Yan

AU - Dilbeck, Tristan

AU - Bretton, Andrew J.

AU - Meeker, David S.

AU - Hanson, Kenneth G.

AU - Albrecht-Schmitt, Thomas E.

PY - 2018/10/15

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N2 - M(TpyNO2)(NO3)3(H2O)·THF (M = La, Nd, Sm, Eu, Tb, Am; TpyNO2 = 4′-nitrophenyl terpyridyl) have been prepared from the reaction of M(NO3)3·nH2O with TpyNO2 in THF. Structural analysis shows that the metal centers are 10-coordinate, providing the first example of AmIII with this coordination number. Further spectroscopic and theoretical evaluation of these complexes reveals utilization of the 5f orbitals in bonding in the AmIII complex. Comparison of Nd-L, Eu-L, and Am-L bond distances demonstrates that some caution should be taken in comparing EuIII versus AmIII in extraction experiments.

AB - M(TpyNO2)(NO3)3(H2O)·THF (M = La, Nd, Sm, Eu, Tb, Am; TpyNO2 = 4′-nitrophenyl terpyridyl) have been prepared from the reaction of M(NO3)3·nH2O with TpyNO2 in THF. Structural analysis shows that the metal centers are 10-coordinate, providing the first example of AmIII with this coordination number. Further spectroscopic and theoretical evaluation of these complexes reveals utilization of the 5f orbitals in bonding in the AmIII complex. Comparison of Nd-L, Eu-L, and Am-L bond distances demonstrates that some caution should be taken in comparing EuIII versus AmIII in extraction experiments.

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JO - Inorganic Chemistry

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ER -

Examination of Structure and Bonding in 10-Coordinate Europium and Americium Terpyridyl Complexes

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