Structural and Spectroscopic Comparison of Soft-Se vs. Hard-O Donor Bonding in Trivalent Americium/Neodymium Molecules

Conrad A.P. Goodwin; Anthony W. Schlimgen; Thomas E. Albrecht-Schönzart; Enrique R. Batista; Andrew J. Gaunt; Michael T. Janicke; Stosh A. Kozimor; Brian L. Scott; Lauren M. Stevens; Frankie D. White; Ping Yang

doi:10.1002/anie.202017186

Structural and Spectroscopic Comparison of Soft-Se vs. Hard-O Donor Bonding in Trivalent Americium/Neodymium Molecules

Conrad A.P. Goodwin, Anthony W. Schlimgen, Thomas E. Albrecht-Schönzart, Enrique R. Batista, Andrew J. Gaunt, Michael T. Janicke, Stosh A. Kozimor, Brian L. Scott, Lauren M. Stevens, Frankie D. White, Ping Yang

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

23 Scopus citations

Abstract

Covalency is often considered to be an influential factor in driving An³⁺ vs. Ln³⁺ selectivity invoked by soft donor ligands. This is intensely debated, particularly the extent to which An³⁺/Ln³⁺ covalency differences prevail and manifest as the f-block is traversed, and the effects of periodic breaks beyond Pu. Herein, two Am complexes, [Am{N(E=PPh₂)₂}₃] (1-Am, E=Se; 2-Am, E=O) are compared to isoradial [Nd{N(E=PPh₂)₂}₃] (1-Nd, 2-Nd) complexes. Covalent contributions are assessed and compared to U/La and Pu/Ce analogues. Through ab initio calculations grounded in UV-vis-NIR spectroscopy and single-crystal X-ray structures, we observe differences in f orbital involvement between Am–Se and Nd–Se bonds, which are not present in O-donor congeners.

Original language	English (US)
Pages (from-to)	9459-9466
Number of pages	8
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	17
DOIs	https://doi.org/10.1002/anie.202017186
State	Published - Apr 19 2021
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2021 Wiley-VCH GmbH

Keywords

actinides
americium
covalency
spectroscopy
structure

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10.1002/anie.202017186

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Goodwin, C. A. P., Schlimgen, A. W., Albrecht-Schönzart, T. E., Batista, E. R., Gaunt, A. J., Janicke, M. T., Kozimor, S. A., Scott, B. L., Stevens, L. M., White, F. D., & Yang, P. (2021). Structural and Spectroscopic Comparison of Soft-Se vs. Hard-O Donor Bonding in Trivalent Americium/Neodymium Molecules. Angewandte Chemie - International Edition, 60(17), 9459-9466. https://doi.org/10.1002/anie.202017186

Goodwin, CAP, Schlimgen, AW, Albrecht-Schönzart, TE, Batista, ER, Gaunt, AJ, Janicke, MT, Kozimor, SA, Scott, BL, Stevens, LM, White, FD & Yang, P 2021, 'Structural and Spectroscopic Comparison of Soft-Se vs. Hard-O Donor Bonding in Trivalent Americium/Neodymium Molecules', Angewandte Chemie - International Edition, vol. 60, no. 17, pp. 9459-9466. https://doi.org/10.1002/anie.202017186

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abstract = "Covalency is often considered to be an influential factor in driving An3+ vs. Ln3+ selectivity invoked by soft donor ligands. This is intensely debated, particularly the extent to which An3+/Ln3+ covalency differences prevail and manifest as the f-block is traversed, and the effects of periodic breaks beyond Pu. Herein, two Am complexes, [Am{N(E=PPh2)2}3] (1-Am, E=Se; 2-Am, E=O) are compared to isoradial [Nd{N(E=PPh2)2}3] (1-Nd, 2-Nd) complexes. Covalent contributions are assessed and compared to U/La and Pu/Ce analogues. Through ab initio calculations grounded in UV-vis-NIR spectroscopy and single-crystal X-ray structures, we observe differences in f orbital involvement between Am–Se and Nd–Se bonds, which are not present in O-donor congeners.",

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author = "Goodwin, {Conrad A.P.} and Schlimgen, {Anthony W.} and Albrecht-Sch{\"o}nzart, {Thomas E.} and Batista, {Enrique R.} and Gaunt, {Andrew J.} and Janicke, {Michael T.} and Kozimor, {Stosh A.} and Scott, {Brian L.} and Stevens, {Lauren M.} and White, {Frankie D.} and Ping Yang",

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doi = "10.1002/anie.202017186",

language = "English (US)",

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AU - Schlimgen, Anthony W.

AU - Albrecht-Schönzart, Thomas E.

AU - Batista, Enrique R.

AU - Gaunt, Andrew J.

AU - Janicke, Michael T.

AU - Kozimor, Stosh A.

AU - Scott, Brian L.

AU - Stevens, Lauren M.

AU - White, Frankie D.

AU - Yang, Ping

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N2 - Covalency is often considered to be an influential factor in driving An3+ vs. Ln3+ selectivity invoked by soft donor ligands. This is intensely debated, particularly the extent to which An3+/Ln3+ covalency differences prevail and manifest as the f-block is traversed, and the effects of periodic breaks beyond Pu. Herein, two Am complexes, [Am{N(E=PPh2)2}3] (1-Am, E=Se; 2-Am, E=O) are compared to isoradial [Nd{N(E=PPh2)2}3] (1-Nd, 2-Nd) complexes. Covalent contributions are assessed and compared to U/La and Pu/Ce analogues. Through ab initio calculations grounded in UV-vis-NIR spectroscopy and single-crystal X-ray structures, we observe differences in f orbital involvement between Am–Se and Nd–Se bonds, which are not present in O-donor congeners.

AB - Covalency is often considered to be an influential factor in driving An3+ vs. Ln3+ selectivity invoked by soft donor ligands. This is intensely debated, particularly the extent to which An3+/Ln3+ covalency differences prevail and manifest as the f-block is traversed, and the effects of periodic breaks beyond Pu. Herein, two Am complexes, [Am{N(E=PPh2)2}3] (1-Am, E=Se; 2-Am, E=O) are compared to isoradial [Nd{N(E=PPh2)2}3] (1-Nd, 2-Nd) complexes. Covalent contributions are assessed and compared to U/La and Pu/Ce analogues. Through ab initio calculations grounded in UV-vis-NIR spectroscopy and single-crystal X-ray structures, we observe differences in f orbital involvement between Am–Se and Nd–Se bonds, which are not present in O-donor congeners.

KW - actinides

KW - americium

KW - covalency

KW - spectroscopy

KW - structure

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Structural and Spectroscopic Comparison of Soft-Se vs. Hard-O Donor Bonding in Trivalent Americium/Neodymium Molecules

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