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. 2025 Jan 9;44(2):439-446.
doi: 10.1021/acs.organomet.4c00472. eCollection 2025 Jan 27.

Neptunium Pyridine Dipyrrolide Complexes

Leyla R Valerio  1 , Andrew W Mitchell  2 , Lauren M Lopez  2 , Matthias Zeller  2 , Suzanne C Bart  2 , Ellen M Matson  1
Affiliations

Neptunium Pyridine Dipyrrolide Complexes

Leyla R Valerio et al. Organometallics. .

Abstract

Two pyridine dipyrrolide neptunium(IV) complexes, (MesPDPPh)NpCl2(THF) and Np(MesPDPPh)2, where (MesPDPPh)2- is the doubly deprotonated form of 2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine, have been prepared. Characterization of the complexes has been performed through a combination of solid- and solution-state methods, including single-crystal X-ray diffraction and electronic absorption and nuclear magnetic resonance spectroscopies. Collectively, these data confirm the formation of the mono- and bis-ligated species. Electrochemistry of a series of bis-ligated actinide complexes, An(MesPDPPh)2 (An = Th, U, Np), is presented.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
1H NMR spectrum (400 MHz) of 1-Np stacked with 1-U for comparison collected in C6D6 at room temperature (∼21 °C). For full assignments, see the Supporting Information.
Scheme 1
Scheme 1. Synthesis of (MesPDPPh)AnCl2(THF) Complexes (1-Th, 1-U, 1-Np)
Figure 2
Figure 2
Molecular structure of (MesPDPPh)NpCl2(THF) (1-Np) is shown with 30% probability ellipsoids. Hydrogen atoms have been omitted for clarity.
Figure 3
Figure 3
Electronic absorption spectra for (MesPDPPh)NpCl2(THF) (1-Np), with 1-Th and 1-U included for comparison. Spectra were collected at room temperature in dichloromethane.
Scheme 2
Scheme 2. Synthesis of An(MesPDPPh)2 Complexes (1-Th, 1-U, 1-Np)
Figure 4
Figure 4
1H NMR spectrum (400 MHz) of 2-Np stacked with 2-U for comparison was collected in C6D6 at room temperature (∼21 °C). For full assignments, see the Supporting Information.
Figure 5
Figure 5
Electronic absorption spectra in the visible region for Np(MesPDPPh)2 (2-Np), with 2-Th and 2-U included for comparison. Spectra were collected at room temperature in dichloromethane.
Figure 6
Figure 6
Cyclic voltammograms of Th(MesPDPPh)2, U(MesPDPPh)2, and Np(MesPDPPh)2 recorded in DCM (1 mM analyte, 0.1 M TBAPF6, scan rate = 200 mV s–1).
See this image and copyright information in PMC

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