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Complexation of glutarimidedioxime with Fe(III),

Cu(II), Pb(II), and Ni(II), the competing ions for the
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Cite this: Dalton Trans., 2013, 42, 14621

sequestration of U(VI) from seawater†

Xiaoqi Sun,a,b Chao Xu,a,c Guoxin Tiana and Linfeng Rao*a

Received 2nd July 2013,
Accepted 6th August 2013
DOI: 10.1039/c3dt51767e
www.rsc.org/dalton
The stability constants of the complexes of Fe(III), Cu(II), Pb(II), and Ni(II) with glutarimidedioxime, a ligand
that has significant implications in the sequestration of uranium from seawater with amidoxime-based
sorbents, were determined by potentiometry. The enthalpies of complexation for the Fe(III)/glutarimide-
dioxime complexes were determined by microcalorimetry. Compared with the data for the complexation
of U(VI) with glutarimidedioxime in the literature, Fe(III) forms much stronger complexes with glutarimide-
dioxime and is expected to affect the efficiency of uranium sequestration from seawater by competing
for the sorption sites of the amidoxime-based sorbents. The structures of two Fe(III)/glutarimidedioxime
complexes were identified by single-crystal X-ray diffractometry, and helped to interpret the stronger
complexation of Fe(III) with glutarimidedioxime than that of U(VI).

Introduction Table 1 Concentrations of some metal ions in seawater6

Sequestration of uranium from seawater has recently become a
subject of research1–4 with substantially high interest because
of the huge demand in uranium as a fuel in the nuclear energy
systems and the massive quantities of uranium in seawater.
Though the concentration of uranium in seawater is extremely
low (3.3 μg L−1),1,5 the total amount of uranium is estimated to
be 4.5 billion metric tons in the ocean, more than a thousand
times as much as that in terrestrial ores. However, extraction
of uranium from seawater is extremely challenging not only
because uranium is present in very low concentrations, but
also because many other cations including transition metal
ions also exist in seawater, some of which are in concen-
trations higher than or comparable to that of uranium
(Table 1). As a result, the process for the sequestration of
uranium must be very efficient and highly selective.
Many technologies have been investigated for the sequestra-
tion of uranium from seawater, including solvent extraction,7,8
a
Chemical Sciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron
Rd., Berkeley, California 94720, USA. E-mail: lrao@lbl.gov; Fax: +01 5104865596;
Tel: +01 5104865427
b
Xiamen Institute of Rare Earth Materials, Chinese Academy of Sciences,
Xiamen 361021, China
c
Institute of Nuclear and New Energy Technology, Tsinghua University,
Beijing 100084, China
† Electronic supplementary information (ESI) available: Experimental conditions
of spectrophotometry and potentiometry, the CIF and Checkcif files for FeHACl2
and FeHA2·8H2O. CCDC 947989 and 947990. For ESI and crystallographic data
in CIF or other electronic format see DOI: 10.1039/c3dt51767e
Element Concentration (mg kg−1)
U 0.0033
Na 10 800
K 392
Mg 1290
Ca 411
Fe 0.0034
Cu 0.0009
Ni 0.0066
Pb 0.00003
ion exchange,9,10 membrane separation,11,12 flotation,13 and
sorption.14 Among these, sorption of uranium by fiber
materials functionalized with amidoxime-related ligand
groups has shown the best promise. Kilogram quantities of
uranium were collected in 30-day marine tests in Japan.3
Based on the most optimistic estimate, the cost of collect-
ing uranium from seawater with the amidoxime-based sor-
bents currently developed in Japan is at least 2–3 times the
spot market price of uranium.3 To make the process economi-
cally competitive, the sorption efficiency for uranium and the
selectivity over other metal ions must be improved. Thermo-
dynamic and structural studies should be conducted to evalu-
ate the binding strength of amidoxime-related ligands with U(VI)
and other major metal ions, and provide guidance in
designing new ligands and optimizing the preparation of sor-
bents. Recent studies from this group have shown that U(VI)
forms fairly strong complexes with glutarimidedioxime
(Fig. 1), a probable ligand configuration on the amidoxime-

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Paper
Fig. 1 Glutarimidedioxime (H2A).
based sorbents at seawater pH and carbonate concentrations.15
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To provide thermodynamic data to help evaluate the compe-
tition between U(VI) and other metal ions in the sequestration
process, the present study has been conducted with a focus on
the complexation of glutarimidedioxime with major transition
metal ions (Fe, Cu, and Ni) and Pb, because the seawater tests
in Japan showed that the sorption coefficients of these ions
are comparable or even higher than that of U(VI).2,3 Stability
constants of the complexes for Fe(III), Cu(II), Pb(II), and Ni(II)
were determined. Because Fe(III) was found to form the stron-
gest complexes, further thermodynamic and structural studies
of Fe(III)/glutarimidedioxime complexes, including microcalori-
metry and single crystal X-ray diffractometry, were performed.
Data from this work, in conjunction with the previous data on
the complexation of U(VI) with glutarimidedioxime, allow a
quantitative evaluation of the competition between U(VI) and
these metal ions.
In this paper, the glutarimidedioxime ligand is denoted as H2A,
where A2− represents the fully deprotonated glutarimidedioxime.
Experimental
Chemicals
All chemicals were of reagent-grade or higher. Boiled/cooled
Milli-Q water was used in the preparation of solutions. All
experiments were conducted at 25 °C and an ionic strength of
0.5 M (NaCl). Glutarimidedioxime (H2A) was synthesized, puri-
fied, and characterized by 1H NMR and potentiometric titra-
tions as described elsewhere.15 Stock solutions of Fe(III), Cu(II),
Pb(II), and Ni(II) in hydrochloric acid were prepared by dissol-
ving corresponding chlorides in aqueous solutions of HCl. The
concentrations of Fe(III), Cu(II), Pb(II), and Ni(II) in the stock
solutions were determined by complexometry using standard
EDTA (ethylenediaminetetraacetic acid) as the titrant under
different conditions: for Fe(III), PAN (1-(2-pyridylazo)-2-
naphthol) as the indicator (yellow to red) in pH 4.8 acetate
buffer; for Cu(II), murexide as the indicator (orange to red) in
pH 4 acetate buffer; for Ni(II), murexide as the indicator (orange
to colorless) in pH 10 ammonium buffer; for Pb(II), xylenol
orange as the indicator (red to brilliant yellow) in pH 6 hexa-
methylenediamine solution. The concentrations of hydrochloric
acid in the stock solutions were determined by Gran’s titration.16
Potentiometry
Potentiometric titrations were conducted using an automatic
titration system consisting of a glass titration cell, a Metrohm
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Dalton Transactions
pH meter (Model 713) equipped with a Ross combination pH
electrode (Orion Model 8102), a Metrohm dosimat (Model
765), and a computer. The temperature of the titration cell was
maintained at 25.0 ± 0.1 °C by an external circulating water
bath. An inert atmosphere, Ar, was used to prevent the sorp-
tion of CO2 by the solution in the cell during the titration. The
original inner solution (3 M KCl) of the electrode was replaced
with 1 M NaCl to reduce the electrode junction potential.
In the potentiometric titrations, the concentration of hydro-
gen ions was determined from the measured electromotive
force (EMF, in millivolts). The EMF in acidic and basic regions
can be expressed by eqn (1) and (2), respectively.
E ¼ E 0 þ RT=F ln½Hþ  þ γ H ½Hþ  ð1Þ
E ¼ E 0 þ RT=F lnðQw =½OH Þ þ γ OH ½OH  ð2Þ
where R is the gas constant, F is the Faraday constant, and T is
the temperature in K. Qw = [H+][OH−]. The last terms, γH[H+] in
eqn (1) and γOH[OH−] in eqn (2), are the electrode junction
potentials for the hydrogen ion or the hydroxide ion (ΔEj,H+ or
ΔEj,OH−), assumed to be proportional to the concentration of
the hydrogen or hydroxide ions. Prior to each titration, an
acid/base titration with standard HCl and NaOH was per-
formed to obtain the electrode parameters of E0, γH, and γOH.
These parameters allowed the calculation of hydrogen ion con-
centrations from the EMF in the subsequent titration. For each
of the four metal ions, multiple titrations were conducted with
solutions of different concentrations of the metal ions (CM),
the glutarimidedioxime ligand (CA), and total proton (CH). The
potentiometric titration data were analyzed to obtain the stabi-
lity constants of the complexes between the metal ions and
glutarimidedioxime by the Hyperquad 2008 program.17
Microcalorimetry
The enthalpy of the complexation of Fe(III) with glutarimide-
dioxime at 25 °C was determined using an isothermal titration
microcalorimeter (ITC 4200, Calorimetry Sciences Corp.).
Detailed information on the microcalorimeter and its cali-
bration has been provided previously.15,18 Multiple titrations
were performed to reduce the uncertainty of results using
different CM, CA, and CH. The reaction heats measured by
microcalorimetry were used, in conjunction with the equili-
brium constants obtained by potentiometry, to calculate
the enthalpy of complexation with the computer program
HypDeltaH.18
Single-crystal X-ray diffractometry
Two crystals of Fe(III)/glutarimidedioxime complexes, Fe(HA)-
Cl2 and FeHA2·8H2O, were obtained. The red plate crystal of
the 1 : 1 metal–ligand complex, Fe(HA)Cl2, was obtained by
recrystallization from an aqueous solution containing FeCl3
and H2A (molar ratio = 1 : 1) with excess pyridine. The red
crystal of the 1 : 2 metal–ligand complex, FeHA2·8H2O, was
obtained by slow evaporation from 1 mL solution containing
Fe2(SO4)3 and Na2A (molar ratio = 1 : 2.1). The crystals were
mounted on a Cryoloop with Paratone oil. Data were collected
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in a nitrogen gas stream at 100(2) K using phi and omega Results

scans, on the diffractometer in the X-ray Crystallography Facil-
ity of College of Chemistry, University of California at Berkeley.
The data were integrated using the Bruker SAINT program and
scaled using the TWINABS program. Solution by direct
methods (SIR-97) produced a complete heavy-atom phasing
model consistent with the proposed structure. All non-hydro-
gen atoms were refined anisotropically by full-matrix least-
squares (SHELXL-2013) utilizing the full data set. All hydrogen
atoms were placed using a riding model. Their positions were
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Stability constants
Detailed conditions of the potentiometric titrations are pro-
vided in ESI.† Representative titrations, one for each metal ion,
are shown in Fig. 2. Best models to fit the potentiometric data
include the formation of a number of complexes between
glutarimidedioxime and the metal ions, including MA, MHA,
MA2, MHA2 and MH2A2, as represented by eqn (3) (the electri-
cal charges of the species are omitted for clarity):

constrained relative to their parent atom using the appropriate

M þ mH þ nA ¼ MHm An ð3Þ
HFIX command in SHELXL-2013. Details of the crystallo-
graphic data and structure refinement are shown in Table 2. where m = 0, 1, or 2, n = 1 or 2. For the titrations of the Fe(III)/
glutarimidedioxime system, it was necessary to include a
species denoted as FeH−1A22− (or Fe(OH)A22−) in the model to
improve the goodness of fitting in the region of high pCH
(>10). This species could be a ternary hydrolyzed complex as
Table 2 Crystallographic data and structure refinement
Fe(OH)A22− or a binary Fe(III)/glutarimidedioxime complex as
Identification code Fe(HA)Cl2 FeHA2·8H2O FeH−1A22− resulting from the further deprotonation of FeA2−.
In the calculation, the values of the protonation constants of
Empirical formula C5H8.62Cl2FeN3O2.25 C10H31FeN6O12
Formula weight 273.52 483.26 glutarimidedioxime were taken from the previous study15 and
Temperature 100(2) K 100(2) K confirmed by additional potentiometric titrations at 25 °C and
Wavelength 0.71073 Å 0.71073 Å in 0.5 M NaCl in this study. The calculated stability constants
Crystal system Orthorhombic Monoclinic
Space group P212121 P2(1)/c of the metal complexes are given in Table 3.
Unit cell a = 9.3249(5) Å α = 90° a = 14.102(4) Å α = 90°
dimensions b = 9.4984(4) Å β = 90° b = 11.929(3) Å Enthalpy of complexation
β = 91.976(3)°
c = 22.7056(8) Å γ = 90° c = 12.857(3) Å γ = 90° Detailed conditions of the microcalorimetric titrations are pro-
Volume 2011.07(15) Å3 2161.5(9) Å3
vided in ESI.† Fig. 3 shows a representative titration of Fe(III)/
Z 8 4
Density 1.807 Mg m−3 1.485 Mg m−3
(calculated)
Absorption 2.005 mm−1 0.765 mm−1
coefficient
F(000) 1101 1020
Crystal size 0.08 × 0.06 × 0.02 mm3 0.12 × 0.10 ×
0.04 mm3
Crystal color/habit Red plate Red plate
Theta range for 1.794 to 25.358° 1.44 to 25.42°
data collection
Index ranges −11 ≤ h ≤ 11, −11 ≤ k ≤ −16 ≤ h ≤ 16, −14 ≤ k
11, −27 ≤ l ≤ 27 ≤ 14, −15 ≤ l ≤ 15
Reflections 26 858 47 520
collected
Independent 14 493 [R(int) = 0.0633] 3972 [R(int) = 0.0252]
reflections
Completeness to 99.9% 100.0%
theta = 25.00°
Absorption Semi-empirical from Semi-empirical from
correction equivalents equivalents
Max. and min. 0.929 and 0.789 0.9701 and 0.9138
transmission
Refinement Full-matrix least-squares Full-matrix least-
method on F2 squares on F2
Data/restraints/ 14 493/0/246 3972/0/262
parameters
Goodness-of-fit on 0.975 1.062
F2
Fig. 2 Potentiometric titration for the complexation of glutarimidedioxime
Final R indices R1 = 0.0479, wR2 = 0.0971 R1 = 0.0247,
[I > 2σ(I)] wR2 = 0.0653 (H2A) with metal ions, I = 0.5 M NaCl, t = 25 °C. Titration conditions are provided
R indices (all data) R1 = 0.0605, wR2 = 0.1031 R1 = 0.0265, in ESI.† Gray circles – experimental pCH, dashed black line – fitted pCH (right
wR2 = 0.0669 y-axis). Solid color lines – the percentages of metal complexes with H2A (left
Absolute structure 0.028(16) y-axis); Fe: 1 – Fe(HA)2+, 2 – Fe(HA)2+, 3 – FeHA2, 4 – FeA2−, 5 – Fe(OH)A22−;
parameter Cu: 1 – Cu2+, 2 – Cu(HA)+, 3 – CuA, 4 – CuHA2−, 5 – CuA22−; Pb: 1 – Pb2+, 2
Largest diff. peak 0.744 and −0.431 e Å−3 0.420 and – Pb(HA)+, 3 – PbA, 4 – PbHA2−, 5 – PbA22−; Ni: 1 – Ni2+, 2 – NiA, 3 – NiHA2−,
and hole −0.440 e Å−3 4 – NiA22−.

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Table 3 Stability constants of the glutarimidedioxime complexes with Fe(III), Cu(II), Pb(II), and Ni(II) in comparison with U(VI) (25 °C, I = 0.5 M NaCl). Data for U(VI) are
from ref. 15

log β

Reactions UO22+ Fe3+ Cu2+ Pb2+ Ni2+

Mj+ + A2− = MAj−2 17.8 ± 1.1 18.94 ± 0.05 14.28 ± 0.02 10.32 ± 0.03
Mj+ + H+ + A2− = M(HA)j−1 22.7 ± 1.3 25.66 ± 1.09 22.71 ± 0.04 21.78 ± 0.05
Mj+ + 2A2− = MA2j−4 27.5 ± 2.3 36.02 ± 1.07 24.45 ± 0.11 19.38 ± 0.22 16.74 ± 0.07
Mj+ + H+ + 2A2− = MHA2j−3 36.8 ± 2.1 43.94 ± 1.08 35.77 ± 0.11 29.96 ± 0.23 27.05 ± 0.10
Mj+ + 2H+ + 2A2− = MH2A2j−2 43.0 ± 1.1 49.71 ± 1.08
Mj+ + H2O + 2A2− = M(OH)A2j−5 + H+ 25.73 ± 1.08
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Table 4 Enthalpy and entropy of Fe(III)/glutarimidedioxime complexation

(25 °C, I = 0.5 M NaCl)

Reactiona ΔH (kJ mol−1) ΔS (J K−1 mol−1)

H+ + A2− = HA− −36.1 ± 0.5 110 ± 2

2H+ + A2− = H2A −69.7 ± 0.9 202 ± 3
3H+ + A2− = H3A+ −77 ± 6 218 ± 14
Fe3+ + H+ + A2− = FeHA2+ −63 ± 2 283 ± 28
−
3+ 2−
Fe + 2A = FeA2 −64 ± 3 479 ± 32
Fe3+ + H+ + 2A2− = FeHA2 −91 ± 3 536 ± 31
Fe3+ + 2H+ + 2A2− = FeH2A2+ −113 ± 3 573 ± 31
3+ 2−
Fe + H2O + 2A = Fe(OH)A2 + H2− +
−50 ± 3 325 ± 30
a
Enthalpy and entropy of protonation are from ref. 15.

Fig. 3 Calorimetric titration of the complexation of Fe(III) with glutarimidedi-

oxime (H2A), I = 0.5 M NaCl, t = 25 °C. Initial solution: V = 0.900 mL, CFe =
0.911 mM, CA = 1.89 mM, CH = 4.08 mM; Titrant: 0.0213 M NaOH (5.0 μL per
addition). (upper) thermogram; (lower) total heat (right y axis, O – experimental,
dashed line – fit) and speciation of Fe(III) (left y axis) vs. the titrant volume.
1 – Fe(HA)2+, 2 – Fe(HA)2+, 3 – FeHA2, 4 – FeA2−, 5 – Fe(OH)A22−.

Fig. 4 Crystal structures of [Fe(HA)Cl2] (top, only 1 component of the twinned

glutarimidedioxime complexation. The total reaction heat,
Q,r,j, as well as the distribution of Fe(III) species, is shown as a
function of the titrant volume. From the reaction heat and the
stability constants of the Fe(III) complexes, the enthalpies as
well as the entropies of complexation were calculated and
listed in Table 4.
Crystal structures of Fe(III)/glutarimidedioxime complexes
Single-crystal structures of the 1 : 1 and 1 : 2 metal–ligand com-
plexes, Fe(HA)Cl2 and FeHA2·8H2O, are shown in Fig. 4. For
the Fe(HA)Cl2 complex, indexing and unit cell refinement
(CELLNOW) indicated a non-merohedral twinned but primi-
tive, orthorhombic lattice, consisting of 2 components. The
space group was found to be P212121 (No. 19). The twinned
crystal is shown) and [FeHA2·8H2O] (bottom). Water molecules are omitted for
clarity.
data were integrated simultaneously using the Bruker SAINT
software program and scaled using the TWINABS software
program. Data were not merged due to the presence of the 2
component twin. For the FeHA2·8H2O complex that crystalized
in a primitive, monoclinic lattice, the space group was found
to be P2(1)/c (No. 14). Major bond lengths and angles of the
two structures are summarized in Table 5.
The bond lengths of Fe–O and Fe–N are of particular inter-
est because, in comparison with the U–O and U–N bond
lengths in the UO2(HA)2 complex,15 they have demonstrated
the stronger binding of Fe(III) with glutarimidedioxime than

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Table 5 Major bond distances (Å) and angles (°) in the Fe(III)/glutarimide- shorter than the U–O and U–N bonds in the glutarimidedi-
dioxime complexes oxime complexes. Because the Fe(III) atomic radius (0.55 Å and
0.645 Å for low spin and high spin complexes, respectively) is
Fe(HA)Cl2 FeHA2·8H2O
only 0.18 Å (low-spin) or 0.085 Å (high-spin) shorter than the
N(2)–Fe(1) 2.005(8) 2.0298(13) U(VI) atomic radius (0.73 Å), the crystal structures have indeed
N(5)–Fe(1) 2.0035(13) demonstrated much stronger covalent bonding of glutarimide-
O(1)–Fe(1) 2.017(7) 2.0465(11)
O(2)–Fe(1) 2.021(6) 2.0569(12) dioxime with Fe(III) than U(VI).
O(3)–Fe(1) 2.0268(11) The interpretation of the order of binding strength for
O(4)–Fe(1) 2.0692(11) Cu(II), Ni(II), and Pb(II) may not be that straightforward. In fact,
Cl(1)–Fe(1) 2.220(3)
Cl(2)–Fe(1) 2.227(3) these ions preferably form complexes with different coordi-
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∠N(2)–Fe(1)–O(1) 75.7(3) 74.79(5) nation numbers and geometry. For example, Cu(II) tends to
∠N(2)–Fe(1)–O(2) 75.3(3) 74.55(5) form 4-coordinated square-planar or 5-coordinated square pyr-
∠N(5)–Fe(1)–O(4) 73.79(5)
∠N(5)–Fe(1)–O(3) 76.03(5) amidal complexes with mixed O,N-donor ligands such as
Schiff bases.20 Pb(II) often forms 6-coordinated octahedral
complexes while the 4-coordinated square-planar complexes of
that of U(VI), in agreement with the thermodynamic trend in Ni(II) are most numerous.19 The order of binding strength for
the binding strength measured by potentiometry. these ions might be a composite result of all the affecting
factors including ionic radii, coordination number, geometry,
as well as the nature of the bonding orbitals. For example,
Discussion Pb(II) forms weaker complexes with glutarimidedioxime than
Fe(III), U(VI), and Cu(II), probably due to, among all factors, its
Binding strengths of glutarimidedioxime with Fe(III), Cu(II), lower charge density. In the case of Ni(II), it is probably
Pb(II), and Ni(II), in comparison with U(VI) difficult for the most preferred square-planar geometry to
Data in Table 3 show a general sequence of binding strength accommodate the tridentate ligands such as glutarimidedi-
of glutarimidedioxime as: Fe(III) > U(VI) ∼ Cu(II) > Pb(II) > Ni(II). oxime so that the Ni(II) complexes are expected to be weaker
The binding strength of glutarimidedioxime with Fe(III) is than other complexes.
much stronger than that with U(VI): the stability constants of Because of the much stronger complexation of glutarimide-
the Fe(III) complexes, FeHA2+, FeA2−, FeHA2 and FeH2A2+, are 3, dioxime with Fe(III) than U(VI) and the higher molar concen-
8.5, 7, and 6.7 orders of magnitude higher, respectively, than tration of Fe(III) than U(VI) in seawater ([Fe] = 3.4 ppb ≈ 6.1 ×
those of the corresponding U(VI) complexes. The order of the 10−8 M; ([U] = 3.3 ppb ≈ 1.4 × 10−8 M), Fe(III) is expected to be
binding strength can be rationalized by taking into consider- a very strong competitor with U(VI) in the collection of U(VI)
ation a few factors including the ionic radii, the effective from seawater by amidoxime-based sorbents. A speciation
charge, the nature of the bonding orbitals, and the steric diagram (Fig. 5), calculated with the stability constants and
requirements in these complexes. the concentrations of Fe(III), U(VI), and total carbonate in sea-
For the coordination number of 6, the ionic radii of the water, indicated that the dominant species of Fe(III) and U(VI)
ions under study decrease in the order: Pb(II) (1.19 Å) > Cu(II)
(0.73 Å) ∼ U(VI) (0.73 Å) > Ni(II) (0.69 Å) > Fe(III) (0.55 Å for “low-
spin” complexes and 0.645 Å for “high-spin” complexes).19
Obviously, the highest binding strength of Fe(III) with glutari-
midedioxime results from its highest ionic charge and smal-
lest radius in this series. Besides, the much stronger binding
strength of Fe(III) than U(VI) could also originate from the
difference in the nature of the binding. In the Fe(III) complex,
participation of the d-orbitals of Fe(III) allows a large overlap
with the donor atom orbitals (from O and N), forming strong
covalent bonds. In contrast, in the U(VI) complex, the f-orbitals
are less extended and less overlapped with the donor atom
orbitals, forming coordination bonds with lower covalency.
Consequently, Fe(III) forms much stronger complexes with glu-
tarimidedioxime than U(VI). The crystal structures of Fe(HA)Cl2
and FeHA2·8H2O from this work (Fig. 4 and Table 5) and that
of UO2(HA)2 from the previous work15 support this argument.
In the glutarimidedioxime complexes, the Fe–O and Fe–N
bond distances range from 2.00 to 2.06 Å (Table 5), while the Fig. 5 Speciation of U(VI) and Fe(III) in the presence of 0.01 M glutarimidedi-
U–O and U–N bond distances range from 2.43 to 2.56 Å,15 oxime as a function of pH. CA = 0.01 M, CU = 3.3 ppb, CFe = 3.4 ppb, Ccarbonate =
meaning that the Fe–O and Fe–N bonds are 0.43–0.50 Å 0.0023 M.

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are FeA2− and UO2HA2−, respectively, at the seawater pH 8.3,
and that, if the amount of ligand is sufficient for complexing
both Fe(III) and U(VI), the molar concentration of FeA2− is more
than 4 times that of UO2HA2−. As a result, the number of
effective sites that could be available for the sorption of
uranium would be reduced because a larger portion of the
sorbent sites is occupied by Fe(III). If the number of effective
sites are limited and insufficient to accommodate all Fe(III)
and U(VI), the molar ratio of sorbed Fe(III) to U(VI) could be
even higher than 4 because Fe(III) forms much stronger com-
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plexes than U(VI). In fact, the sorption experiments in Japan
using seawater showed that the distribution coefficient of
Fe(III) was about 10 times that of U(VI).2,3
Effect of temperature on the complexation of
glutarimidedioxime with Fe(III) – implications on the
selectivity of amidoxime-based sorbents at different
temperatures
In a previous study,15 the major overall reaction for the inter-
actions of glutarimidedioxime with U(VI) was written as eqn
(4), based on the thermodynamic parameters on the speciation
of carbonate,21 the glutarimidedioxime ligand and its com-
plexes with U(VI).
UO2 ðCO3 Þ3 4 þ 2H2 A ¼ UO2 HA2  þ 3HCO3 
− 4−
Using the enthalpy values for HCO3 and UO2(CO3)3 in
the literature21,22 and for H2A and UO2(HA)A− from the pre-
vious work,15 the enthalpy of reaction (4) was calculated to be
+16.7 kJ mol−1.15 This means that the overall sequestration of
U(VI) from seawater by glutarimidedioxime is endothermic,
and that the efficiency of sequestration of U(VI) should be
enhanced at higher temperatures.
In the case of Fe(III), data in the literature21,23 imply that, in
the pH region around 8–9 and in the presence of carbonate,
Fe(III) could probably exist as Fe(OH)3(aq) and/or Fe(OH)CO3(aq).
Though the enthalpies of the formation of these species are
not known, the dissociation of these species is expected to be
highly endothermic. Therefore, for the probable overall reac-
tions of (5) or (6), a rough estimate suggests that the enthalpy
of reaction is endothermic:
FeðOHÞ3 ðaqÞ þ 2H2 A þ OH ¼ FeA2  þ 4H2 O
FeðOHÞCO3 ðaqÞ þ 2H2 A þ 2OH
¼ FeA2  þ 3H2 O þ HCO3 
Because the enthalpies of reactions for the overall reactions
of U(VI) and Fe(III) are both endothermic (and probably of
similar magnitude), the sorption of U(VI) and Fe(III) would all
be enhanced at higher temperatures. Consequently, higher
temperatures may not help to improve the selectivity of the
amidoxime-based sorbents for U(VI) over Fe(III).
Coordination modes
A number of crystal structures of transition metal complexes
(Co, Ni, Cu, Mo, Pt, and Fe) with amidoxime-related ligands
14626 | Dalton Trans., 2013, 42, 14621–14627
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Dalton Transactions
were identified in the literature,24–36 but no structures of Fe(III)
complexes with glutarimidedioxime have been reported. In the
recently-reported crystal structures of Fe(III) complexes, a
number of coordination modes were identified in the poly-
nuclear complexes with pyrazine-2-amidoxime (H2pzaox),
[Fe11(μ4-O)7(μ2-O)3(Hpzaox)9(H2O)6Cl]Cl3·5CH3OH·5H2O and
[Fe3(Hpzaox)6]Cl2·10H2O, involving the oxygen and nitrogen
atoms of the oxime, amide, and pyrazine moieties.36
The crystal structures of Fe(III) complexes from this work
(Fig. 4) are the only mono-nuclear Fe(III) complexes with glutar-
imidedioxime that have been reported. In the 1 : 1 metal–
ligand complex (Fe(HA)Cl2), the ligand coordinates to the iron
atom in a tridentate mode through the two oxime oxygen
atoms and the imide nitrogen atom. The proton of the oxime
group is rearranged from the oxygen atom to the nitrogen
atom, and the middle imide group is deprotonated (HA−) to
coordinate to Fe3+. In the 1 : 2 metal–ligand complex (FeHA2),
the two ligand units are not identical: one is HA− and the
other is A2−. Both HA− and A2− are tridentate with two oxime
oxygens and one imido nitrogen coordinating to the center Fe
atom. Similar to the coordination mode in the UO2(HA)2
complex,15 the HA− ligand coordinates to Fe3+ through a conju-
gated system with delocalization of electron density on –O–N–
C–N–C–N–O–, resulting in very strong complexes. However,
ð4Þ difference can be observed in the coordination strength and
mode between the complexes with U(VI) and Fe(III). As dis-
cussed in a previous section, the difference in the bond dis-
tances between the Fe–O/Fe–N bonds in Fe(III) complexes
(2.00–2.06 Å) and the U–O/U–N bonds in UO2(HA)2
(2.43–2.56 Å)15 (Table 5) is 0.43–0.50 Å, much larger than the
difference in the atomic radii between Fe(III) and U(VI) (0.18 Å
for low-spin Fe(III) – 0.085 Å for high-spin Fe(III)). This means,
the crystal structures of Fe(III)/glutarimidedioxime complexes
from this work indicate that Fe(III) forms much shorter and
stronger covalent bonding with glutarimidedioxime than U(VI).
It is noteworthy that, in contrast to the almost perfectly planar
–O–N–C–N–C–N–O– moieties in the equatorial plane of the
linear UO22+ cation in the UO2(HA)2 complex,15 the –O–N–C–
N–C–N–O– moiety in Fe(HA)Cl2 or FeHA2 deviates slightly from
a plane, probably due to the short ionic radius of Fe3+ and the
steric hindrance resulting from the octahedral coordination of
ð5Þ Fe3+.
ð6Þ Conclusion
Thermodynamic data from this work show that the binding
strength of glutarimidedioxime with major transition metal
ions, Pb(II), and U(VI) cations follows the order: Fe(III) > U(VI) ∼
Cu(II) > Pb(II) > Ni(II). This trend in the binding strength
reflects the composite effect of a number of factors including
the effective ionic charge, ionic radii, coordination number
and geometry, and the nature of electronic orbitals participat-
ing in the bonding. The much stronger binding of Fe(III) with
glutarimidedioxime than U(VI) is due to the higher charge
density of Fe(III) and the higher covalency in the Fe(III)/
This journal is © The Royal Society of Chemistry 2013

Dalton Transactions
glutarimidedioxime complexes resulting from the larger over-
lapping of the d-orbitals of Fe(III) with the ligand orbitals.
Because Fe(III) forms much stronger complexes with glutarimide-
dioxime than U(VI) and the molar concentration of Fe(III) is
four times as much as that of U(VI) in seawater, Fe(III) would
compete very strongly with U(VI) for the effective sorption sites
on the amidoxime-based sorbents.
Acknowledgements
Published on 07 August 2013. Downloaded by Seton Hall University on 26/09/2014 12:53:11.
This work was supported by the Uranium Resources Program,
Fuel Cycle Research and Development Program, Office of
Nuclear Energy of the U.S. Department of Energy (DOE) under
Contract No. DE-AC02-05CH11231 at Lawrence Berkeley
National Laboratory (LBNL). The authors are thankful to
Dr Antonio DiPasquale for collecting and analyzing the single-
crystal X-ray diffraction data at the X-ray Crystallography Facil-
ity of College of Chemistry, University of California at Berkeley.
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