Elucidating metal (Zr, Hf, Th, U)-hydride covalency using 1H NMR chemical shifts and density functional calculations

M. Gayanethra Kaumini; Xiaojuan Yu; Steven P. Kelley; Jochen Autschbach; Justin R. Walensky

doi:10.1038/s42004-026-02021-7

Elucidating metal (Zr, Hf, Th, U)-hydride covalency using ¹H NMR chemical shifts and density functional calculations

M. Gayanethra Kaumini
, Xiaojuan Yu
, Steven P. Kelley
, Jochen Autschbach
, Justin R. Walensky

Chemistry

University of Missouri
SUNY Buffalo

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

1 Scopus citations

Abstract

Metal-ligand covalency is not fully understood for the actinides and studies comparing group IV transition metals with isostructural Th and U complexes are limited. Herein, we report the synthesis and characterization of [(C₅Me₅)₂(2,6-ⁱPr₂C₆H₃O)M(H)], M = Hf, Th, and U, which can be compared to the previously reported Zr analog, to explore the differences between transition metal and actinide bonding situations. The ¹H NMR chemical shifts of each complex, including the paramagnetic U(IV) compound, showed reasonable agreement with the computed shifts and benchmark the covalency of the metal-hydride bonds.

Original language	English
Article number	209
Journal	Communications Chemistry
Volume	9
Issue number	1
DOIs	https://doi.org/10.1038/s42004-026-02021-7
State	Published - Dec 2026

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title = "Elucidating metal (Zr, Hf, Th, U)-hydride covalency using 1H NMR chemical shifts and density functional calculations",

abstract = "Metal-ligand covalency is not fully understood for the actinides and studies comparing group IV transition metals with isostructural Th and U complexes are limited. Herein, we report the synthesis and characterization of [(C5Me5)2(2,6-iPr2C6H3O)M(H)], M = Hf, Th, and U, which can be compared to the previously reported Zr analog, to explore the differences between transition metal and actinide bonding situations. The 1H NMR chemical shifts of each complex, including the paramagnetic U(IV) compound, showed reasonable agreement with the computed shifts and benchmark the covalency of the metal-hydride bonds.",

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AU - Kaumini, M. Gayanethra

AU - Yu, Xiaojuan

AU - Kelley, Steven P.

AU - Autschbach, Jochen

AU - Walensky, Justin R.

PY - 2026/12

Y1 - 2026/12

N2 - Metal-ligand covalency is not fully understood for the actinides and studies comparing group IV transition metals with isostructural Th and U complexes are limited. Herein, we report the synthesis and characterization of [(C5Me5)2(2,6-iPr2C6H3O)M(H)], M = Hf, Th, and U, which can be compared to the previously reported Zr analog, to explore the differences between transition metal and actinide bonding situations. The 1H NMR chemical shifts of each complex, including the paramagnetic U(IV) compound, showed reasonable agreement with the computed shifts and benchmark the covalency of the metal-hydride bonds.

AB - Metal-ligand covalency is not fully understood for the actinides and studies comparing group IV transition metals with isostructural Th and U complexes are limited. Herein, we report the synthesis and characterization of [(C5Me5)2(2,6-iPr2C6H3O)M(H)], M = Hf, Th, and U, which can be compared to the previously reported Zr analog, to explore the differences between transition metal and actinide bonding situations. The 1H NMR chemical shifts of each complex, including the paramagnetic U(IV) compound, showed reasonable agreement with the computed shifts and benchmark the covalency of the metal-hydride bonds.

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JO - Communications Chemistry

JF - Communications Chemistry

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ER -

Elucidating metal (Zr, Hf, Th, U)-hydride covalency using ¹H NMR chemical shifts and density functional calculations

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