Synthesis, Spectroscopy, and Theoretical Details of Uranyl Schiff-Base Coordination Complexes

Bonnie E. Klamm; Cory J. Windorff; Cristian Celis-Barros; Matthew L. Marsh; Thomas E. Albrecht-Schmitt

doi:10.1021/acs.inorgchem.9b00477

Synthesis, Spectroscopy, and Theoretical Details of Uranyl Schiff-Base Coordination Complexes

Bonnie E. Klamm, Cory J. Windorff, Cristian Celis-Barros, Matthew L. Marsh, Thomas E. Albrecht-Schmitt

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

30 Scopus citations

Abstract

Two uranyl Schiff-base coordination complexes, UO₂L(MeOH) and UO₂Cl₂(H₂L) {L = N,N′-bis[(4,4′-diethylamino)salicylidene]-1,2-phenylenediamine}, have been synthesized that feature a rigid phenyl backbone. These complexes have been characterized by structural, spectroscopic, and theoretical analysis to offer an electronic structure basis to explain the bonding parameters and stability. Single-crystal X-ray analysis reveals that UO₂L(MeOH) adopts the typical "soft taco confirmation" characteristic of uranyl salophen complexes, whereas UO₂Cl₂(H₂L) features an unusual neutral ligand coordination that contains an internal hydrogen bond between the phenol and imine. Rate constants calculated from electrochemical experiments confirm a quasi-reversible UO₂ ²⁺/UO₂ ⁺ couple. Single-configurational and multiconfigurational methods were used to explore the bonding in UO₂L(MeOH) and UO₂Cl₂(H₂L).

Original language	English
Pages (from-to)	23-31
Number of pages	9
Journal	Inorganic Chemistry
Volume	59
Issue number	1
DOIs	https://doi.org/10.1021/acs.inorgchem.9b00477
State	Published - Jan 6 2020
Externally published	Yes

Funding

We thank the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, U.S. Department of Energy, for supporting the research as part of the Center for Actinide Science and Technology funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award DE-SC0016568. For assistance with FTIR spectroscopy, we thank Drake Beery. We also thank Jenny Yang for fruitful insight about cyclic voltammetry.

Funders	Funder number
Office of Basic Energy Sciences
U.S. Department of Energy
Office of Science	DE-SC0016568
Chemical Sciences, Geosciences, and Biosciences Division

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title = "Synthesis, Spectroscopy, and Theoretical Details of Uranyl Schiff-Base Coordination Complexes",

abstract = "Two uranyl Schiff-base coordination complexes, UO2L(MeOH) and UO2Cl2(H2L) {L = N,N′-bis[(4,4′-diethylamino)salicylidene]-1,2-phenylenediamine}, have been synthesized that feature a rigid phenyl backbone. These complexes have been characterized by structural, spectroscopic, and theoretical analysis to offer an electronic structure basis to explain the bonding parameters and stability. Single-crystal X-ray analysis reveals that UO2L(MeOH) adopts the typical {"}soft taco confirmation{"} characteristic of uranyl salophen complexes, whereas UO2Cl2(H2L) features an unusual neutral ligand coordination that contains an internal hydrogen bond between the phenol and imine. Rate constants calculated from electrochemical experiments confirm a quasi-reversible UO2 2+/UO2 + couple. Single-configurational and multiconfigurational methods were used to explore the bonding in UO2L(MeOH) and UO2Cl2(H2L).",

author = "Klamm, {Bonnie E.} and Windorff, {Cory J.} and Cristian Celis-Barros and Marsh, {Matthew L.} and Albrecht-Schmitt, {Thomas E.}",

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AU - Klamm, Bonnie E.

AU - Windorff, Cory J.

AU - Celis-Barros, Cristian

AU - Marsh, Matthew L.

AU - Albrecht-Schmitt, Thomas E.

PY - 2020/1/6

Y1 - 2020/1/6

N2 - Two uranyl Schiff-base coordination complexes, UO2L(MeOH) and UO2Cl2(H2L) {L = N,N′-bis[(4,4′-diethylamino)salicylidene]-1,2-phenylenediamine}, have been synthesized that feature a rigid phenyl backbone. These complexes have been characterized by structural, spectroscopic, and theoretical analysis to offer an electronic structure basis to explain the bonding parameters and stability. Single-crystal X-ray analysis reveals that UO2L(MeOH) adopts the typical "soft taco confirmation" characteristic of uranyl salophen complexes, whereas UO2Cl2(H2L) features an unusual neutral ligand coordination that contains an internal hydrogen bond between the phenol and imine. Rate constants calculated from electrochemical experiments confirm a quasi-reversible UO2 2+/UO2 + couple. Single-configurational and multiconfigurational methods were used to explore the bonding in UO2L(MeOH) and UO2Cl2(H2L).

AB - Two uranyl Schiff-base coordination complexes, UO2L(MeOH) and UO2Cl2(H2L) {L = N,N′-bis[(4,4′-diethylamino)salicylidene]-1,2-phenylenediamine}, have been synthesized that feature a rigid phenyl backbone. These complexes have been characterized by structural, spectroscopic, and theoretical analysis to offer an electronic structure basis to explain the bonding parameters and stability. Single-crystal X-ray analysis reveals that UO2L(MeOH) adopts the typical "soft taco confirmation" characteristic of uranyl salophen complexes, whereas UO2Cl2(H2L) features an unusual neutral ligand coordination that contains an internal hydrogen bond between the phenol and imine. Rate constants calculated from electrochemical experiments confirm a quasi-reversible UO2 2+/UO2 + couple. Single-configurational and multiconfigurational methods were used to explore the bonding in UO2L(MeOH) and UO2Cl2(H2L).

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Synthesis, Spectroscopy, and Theoretical Details of Uranyl Schiff-Base Coordination Complexes

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