A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO2·M]4+ Cation-Cation Complexes

John W. Freiderich; Adam G. Burn; Leigh R. Martin; Kenneth L. Nash; Aurora E. Clark

doi:10.1021/acs.inorgchem.6b02369

A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO₂·M]⁴⁺ Cation-Cation Complexes

John W. Freiderich, Adam G. Burn, Leigh R. Martin, Kenneth L. Nash, Aurora E. Clark

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

9 Scopus citations

Abstract

The equilibrium constants for [NpO₂·M]⁴⁺ (M = Al³⁺, In³⁺, Sc³⁺, Fe³⁺) in μ = 10 M nitric acid and [NpO₂·Ga]⁴⁺ in μ = 10 M hydrochloric acid media have been determined. The trend in the interaction strength follows: Fe³⁺ > Sc³⁺ ≥ In³⁺ > Ga³⁺ ≫ Al³⁺. These equilibrium constants are compared to those of previously reported values for NpO₂⁺ complexes with Cr³⁺ and Rh³⁺ within the literature. Thermodynamic parameters and bonding modes are discussed, with density functional theory and natural bond orbital analysis indicating that the NpO₂⁺ dioxocation acts as a π-donor with transition-metal cations and a σ-donor with group 13 cations. The small changes in electron-donating ability is modulated by the overlap with the coordinating metal ion’s valence atomic orbitals.

Original language	English
Pages (from-to)	4788-4795
Number of pages	8
Journal	Inorganic Chemistry
Volume	56
Issue number	9
DOIs	https://doi.org/10.1021/acs.inorgchem.6b02369
State	Published - May 1 2017
Externally published	Yes

Funding

K.N. acknowledges support from the Department of Energy (DOE) Office of Nuclear Energy’s Nuclear Energy University Programs for funding of this research (Contract No. 14002 02/Project No. 10-881). A.C. acknowledges support from the U.S. DOE, Office of Science, Heavy Elements program, DE-SC-000-1815, for oversight of the computational studies. This research also used resources of the Oak Ridge Leadership Computing Facility at the Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. DOE under Contract No. DE-AC05-00OR22725.

Funders	Funder number
U.S. Department of Energy
Office of Science	DE-AC05-00OR22725, DE-SC-000-1815
Office of Nuclear Energy
Nuclear Energy University Program	10-881, 14002

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title = "A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO2·M]4+ Cation-Cation Complexes",

abstract = "The equilibrium constants for [NpO2·M]4+ (M = Al3+, In3+, Sc3+, Fe3+) in μ = 10 M nitric acid and [NpO2·Ga]4+ in μ = 10 M hydrochloric acid media have been determined. The trend in the interaction strength follows: Fe3+ > Sc3+ ≥ In3+ > Ga3+ ≫ Al3+. These equilibrium constants are compared to those of previously reported values for NpO2+ complexes with Cr3+ and Rh3+ within the literature. Thermodynamic parameters and bonding modes are discussed, with density functional theory and natural bond orbital analysis indicating that the NpO2+ dioxocation acts as a π-donor with transition-metal cations and a σ-donor with group 13 cations. The small changes in electron-donating ability is modulated by the overlap with the coordinating metal ion{\textquoteright}s valence atomic orbitals.",

author = "Freiderich, {John W.} and Burn, {Adam G.} and Martin, {Leigh R.} and Nash, {Kenneth L.} and Clark, {Aurora E.}",

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doi = "10.1021/acs.inorgchem.6b02369",

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T1 - A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO2·M]4+ Cation-Cation Complexes

AU - Freiderich, John W.

AU - Burn, Adam G.

AU - Martin, Leigh R.

AU - Nash, Kenneth L.

AU - Clark, Aurora E.

PY - 2017/5/1

Y1 - 2017/5/1

N2 - The equilibrium constants for [NpO2·M]4+ (M = Al3+, In3+, Sc3+, Fe3+) in μ = 10 M nitric acid and [NpO2·Ga]4+ in μ = 10 M hydrochloric acid media have been determined. The trend in the interaction strength follows: Fe3+ > Sc3+ ≥ In3+ > Ga3+ ≫ Al3+. These equilibrium constants are compared to those of previously reported values for NpO2+ complexes with Cr3+ and Rh3+ within the literature. Thermodynamic parameters and bonding modes are discussed, with density functional theory and natural bond orbital analysis indicating that the NpO2+ dioxocation acts as a π-donor with transition-metal cations and a σ-donor with group 13 cations. The small changes in electron-donating ability is modulated by the overlap with the coordinating metal ion’s valence atomic orbitals.

AB - The equilibrium constants for [NpO2·M]4+ (M = Al3+, In3+, Sc3+, Fe3+) in μ = 10 M nitric acid and [NpO2·Ga]4+ in μ = 10 M hydrochloric acid media have been determined. The trend in the interaction strength follows: Fe3+ > Sc3+ ≥ In3+ > Ga3+ ≫ Al3+. These equilibrium constants are compared to those of previously reported values for NpO2+ complexes with Cr3+ and Rh3+ within the literature. Thermodynamic parameters and bonding modes are discussed, with density functional theory and natural bond orbital analysis indicating that the NpO2+ dioxocation acts as a π-donor with transition-metal cations and a σ-donor with group 13 cations. The small changes in electron-donating ability is modulated by the overlap with the coordinating metal ion’s valence atomic orbitals.

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A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO₂·M]⁴⁺ Cation-Cation Complexes

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