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

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

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 t...

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Veröffentlicht in:Inorganic chemistry 2017-05, Vol.56 (9), p.4788-4795
Hauptverfasser: Freiderich, John W, Burn, Adam G, Martin, Leigh R, Nash, Kenneth L, Clark, Aurora E
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Sprache:eng
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cation-cation
density functional theory
high ionic strength
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
neptunium
spectrophotometry
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container_end_page 4795
container_issue 9
container_start_page 4788
container_title Inorganic chemistry
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creator Freiderich, John W
Burn, Adam G
Martin, Leigh R
Nash, Kenneth L
Clark, Aurora E
description 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.
doi_str_mv 10.1021/acs.inorgchem.6b02369
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Oak Ridge Leadership Computing Facility (OLCF)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO2·M]4+ Cation–Cation Complexes</atitle><jtitle>Inorganic chemistry</jtitle><addtitle>Inorg. Chem</addtitle><date>2017-05-01</date><risdate>2017</risdate><volume>56</volume><issue>9</issue><spage>4788</spage><epage>4795</epage><pages>4788-4795</pages><issn>0020-1669</issn><eissn>1520-510X</eissn><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+ &gt; Sc3+ ≥ In3+ &gt; Ga3+ ≫ Al3+. These equilibrium constants are compared to those of previously reported values for NpO2 + complexes with Cr3+ and Rh3+ within the literature. 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density functional theory
high ionic strength
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
neptunium
spectrophotometry
title A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO2·M]4+ Cation–Cation Complexes
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