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Updated: May 19, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Comparison of Bonding in Isostructural Cerium and Thorium Parent Amide Complexes
Henry H Wilson1, Xiaojuan Yu2, Thibault Cheisson1
1Vagelos Laboratory for Energy Science and Technology, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
None:
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.
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