Comparison of Bonding in Isostructural Cerium and Thorium Parent Amide Complexes

Henry H. Wilson; Xiaojuan Yu; Thibault Cheisson; Michael R. Gau; Jochen Autschbach; Eric J. Schelter

doi:10.1021/acs.inorgchem.6c00416

Comparison of Bonding in Isostructural Cerium and Thorium Parent Amide Complexes

Henry H. Wilson
, Xiaojuan Yu
, Thibault Cheisson
, Michael R. Gau
, Jochen Autschbach
, Eric J. Schelter

Chemistry

University of Pennsylvania
SUNY Buffalo

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

Abstract

A series of isostructural tetravalent cerium and thorium parent amide (NH₂^–) complexes were synthesized and characterized. The electronic structure of the M–N(amide) bond was investigated using ¹⁵N NMR spectroscopy and DFT calculations in a comparative study of the Na-capped complexes [Na(OEt₂)₂][M(NH₂)(TriNOx)][BAr^F₄], M = Ce (3-Ce), Th (3-Th). The ¹⁵N(amide) resonance in 3-Ce was observed at δ = 192 ppm, approximately 95 ppm downfield of the corresponding resonance in 3-Th (δ = 97 ppm). Computational analysis found that the spin–orbit (SO) heavy atom effect on the amide nitrogen NMR shift was relatively small, and comparable, at Δ_SO = 12/16 ppm for 3-Ce/3-Th. The observed large difference in the ¹⁵N chemical shift for 3-Ce/3-Th is primarily due to differences in paramagnetic shielding generated by the amide lone pairs.

Original language	English
Pages (from-to)	11533-11542
Number of pages	10
Journal	Inorganic Chemistry
Volume	65
Issue number	21
DOIs	https://doi.org/10.1021/acs.inorgchem.6c00416
State	Published - Jun 1 2026

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title = "Comparison of Bonding in Isostructural Cerium and Thorium Parent Amide Complexes",

abstract = "A series of isostructural tetravalent cerium and thorium parent amide (NH2–) complexes were synthesized and characterized. The electronic structure of the M–N(amide) bond was investigated using 15N NMR spectroscopy and DFT calculations in a comparative study of the Na-capped complexes [Na(OEt2)2][M(NH2)(TriNOx)][BArF4], M = Ce (3-Ce), Th (3-Th). The 15N(amide) resonance in 3-Ce was observed at δ = 192 ppm, approximately 95 ppm downfield of the corresponding resonance in 3-Th (δ = 97 ppm). Computational analysis found that the spin–orbit (SO) heavy atom effect on the amide nitrogen NMR shift was relatively small, and comparable, at ΔSO = 12/16 ppm for 3-Ce/3-Th. The observed large difference in the 15N chemical shift for 3-Ce/3-Th is primarily due to differences in paramagnetic shielding generated by the amide lone pairs.",

author = "Wilson, \{Henry H.\} and Xiaojuan Yu and Thibault Cheisson and Gau, \{Michael R.\} and Jochen Autschbach and Schelter, \{Eric J.\}",

note = "Publisher Copyright: {\textcopyright} 2026 The Authors. Published by American Chemical Society. Made available for a limited time for personal research and study only https://pubs.acs.org/page/policy/termsofuse.html.",

year = "2026",

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doi = "10.1021/acs.inorgchem.6c00416",

language = "English",

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T1 - Comparison of Bonding in Isostructural Cerium and Thorium Parent Amide Complexes

AU - Wilson, Henry H.

AU - Yu, Xiaojuan

AU - Cheisson, Thibault

AU - Gau, Michael R.

AU - Autschbach, Jochen

AU - Schelter, Eric J.

N1 - Publisher Copyright: © 2026 The Authors. Published by American Chemical Society. Made available for a limited time for personal research and study only https://pubs.acs.org/page/policy/termsofuse.html.

PY - 2026/6/1

Y1 - 2026/6/1

N2 - A series of isostructural tetravalent cerium and thorium parent amide (NH2–) complexes were synthesized and characterized. The electronic structure of the M–N(amide) bond was investigated using 15N NMR spectroscopy and DFT calculations in a comparative study of the Na-capped complexes [Na(OEt2)2][M(NH2)(TriNOx)][BArF4], M = Ce (3-Ce), Th (3-Th). The 15N(amide) resonance in 3-Ce was observed at δ = 192 ppm, approximately 95 ppm downfield of the corresponding resonance in 3-Th (δ = 97 ppm). Computational analysis found that the spin–orbit (SO) heavy atom effect on the amide nitrogen NMR shift was relatively small, and comparable, at ΔSO = 12/16 ppm for 3-Ce/3-Th. The observed large difference in the 15N chemical shift for 3-Ce/3-Th is primarily due to differences in paramagnetic shielding generated by the amide lone pairs.

AB - A series of isostructural tetravalent cerium and thorium parent amide (NH2–) complexes were synthesized and characterized. The electronic structure of the M–N(amide) bond was investigated using 15N NMR spectroscopy and DFT calculations in a comparative study of the Na-capped complexes [Na(OEt2)2][M(NH2)(TriNOx)][BArF4], M = Ce (3-Ce), Th (3-Th). The 15N(amide) resonance in 3-Ce was observed at δ = 192 ppm, approximately 95 ppm downfield of the corresponding resonance in 3-Th (δ = 97 ppm). Computational analysis found that the spin–orbit (SO) heavy atom effect on the amide nitrogen NMR shift was relatively small, and comparable, at ΔSO = 12/16 ppm for 3-Ce/3-Th. The observed large difference in the 15N chemical shift for 3-Ce/3-Th is primarily due to differences in paramagnetic shielding generated by the amide lone pairs.

UR - https://www.scopus.com/pages/publications/105040847726

U2 - 10.1021/acs.inorgchem.6c00416

DO - 10.1021/acs.inorgchem.6c00416

M3 - Article

C2 - 42148624

AN - SCOPUS:105040847726

SN - 0020-1669

VL - 65

SP - 11533

EP - 11542

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 21

ER -

Comparison of Bonding in Isostructural Cerium and Thorium Parent Amide Complexes

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