Impact of lanthanide ion complexation and temperature on the chemical reactivity of N,N,N',N'-tetraoctyl diglycolamide (TODGA) with the dodecane radical cation

Horne, Gregory P.; Celis-Barros, Cristian; Conrad, Jacy K.; Grimes, Travis S.; McLachlan, Jeffrey R.; Rotermund, Brian M.; Cook, Andrew R.; Mezyk, Stephen P.

doi:10.1039/d3cp01119d

Impact of lanthanide ion complexation and temperature on the chemical reactivity of N,N,N',N'-tetraoctyl diglycolamide (TODGA) with the dodecane radical cation

Journal Article · Fri Jun 09 00:00:00 EDT 2023 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d3cp01119d· OSTI ID:1985789

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Idaho National Laboratory (INL), Idaho Falls, ID (United States)
Colorado School of Mines, Golden, CO (United States)
Idaho National Laboratory (INL), Idaho Falls, ID (United States); Florida International University, Miami, FL (United States)
Florida State University, Tallahassee, FL (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
California State University Long Beach, CA (United States)

The impact of trivalent lanthanide ion complexation and temperature on the chemical reactivity of N,N,N',N'-tetraoctyl diglycolamide (TODGA) with the n-dodecane radical cation (RH˙+) has been measured by electron pulse radiolysis and evaluated by quantum mechanical calculations. Additionally, Arrhenius parameters were determined for the reaction of the non-complexed TODGA ligand with the RH˙⁺ from 10–40 °C, giving the activation energy (E_a = 17.43 ± 1.64 kJ mol^–1) and pre-exponential factor (A = (2.36 ± 0.05) × 10¹³ M^–1 s^–1). The complexation of Nd(III), Gd(III), and Yb(III) ions by TODGA yielded [LnIII(TODGA)3(NO3)3] complexes that exhibited significantly increased reactivity (up to 9.3× faster) with the RH˙⁺, relative to the non-complexed ligand: k([Ln^III(TODGA)₃(NO₃)₃] + RH˙⁺) = (8.99 ± 0.93) × 10¹⁰, (2.88 ± 0.40) × 10¹⁰, and (1.53 ± 0.34) × 10¹⁰ M^–1 s^–1, for Nd(III), Gd(III), and Yb(III) ions, respectively. The rate coefficient enhancement measured for these complexes exhibited a dependence on atomic number, decreasing as the lanthanide series was traversed. Preliminary reaction free energy calculations—based on a model [Ln^III(TOGDA)]³⁺ complex system—indicate that both electron/hole and proton transfer reactions are energetically unfavorable for complexed TODGA. Furthermore, complementary average local ionization energy calculations showed that the most reactive region of model N,N,N',N'-tetraethyl diglycolamide (TEDGA) complexes, [Ln^III(TEGDA)₃(NO₃)₃], toward electrophilic attack is for the coordinated nitrate (NO₃^–) counter anions. Furthermore, it is possible that radical reactions with the complexed NO₃^– counter anions dominate the differences in rates seen for the [Ln^III(TODGA)₃(NO₃)₃] complexes, and are likely responsible for the reported radioprotection in the presence of TODGA complexes.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS)

Grant/Contract Number:: AC07-05ID14517; SC0012704; SC0014664

OSTI ID:: 1985789

Alternate ID(s):: OSTI ID: 1984536

Report Number(s):: BNL-224522-2023-JAAM

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 24 Vol. 25; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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