Chemical assembly of the heteronuclear pivalate complex with the LiI and FeIII ions

Article abstract of DOI:10.1007/s11172-018-2091-x

The heteronuclear complex [Fe₄Li₂(O)₂(Piv)10(H₂O)₂] (1, Piv is the pivalic acid anion) was obtained by refluxing Fe^III pivalates with Li^I pivalates in toluene and isolated as the 1?PhCH₃ solvate with a toluene molecule. According to X-ray diffraction data, complex 1 contains the {Fe₄Li₂O₂} core. The M?ssbauer spectroscopy data indicate that the core comprises para magnetic Fe^III ions in the high-spin state located in the symmetric octahedral environment of oxygen atoms. Thermolysis of 1 studied by simultaneous thermal analysis demonstrated thermal stability of the complex up to 225 °С. The main end product of thermolysis at 600 °С is the mixed oxide LiFe₅O₈.

Full text of DOI:10.1007/s11172-018-2091-x

Russian Chemical Bulletin, International Edition, Vol. 67, No. 3, pp. 449—454, March, 2018
449
Chemical assembly of the heteronuclear pivalate complex
with the LiI and FeIII ions*
I. А. Lutsenko,a М. А. Kiskin,a G. G. Alexandrov,† V. K. Imshennik,b Yu. V. Maksimov,b
A. V. Khoroshilov,a A. S. Goloveshkin,c А. А. Sidorov,a and I. L. Eremenkoa,c
a
N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
31 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax +7 (495) 952 1279. E-mail: irinalu05@rambler.ru
bN. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences,
4 ul. Kosygina, 119991 Moscow, Russian Federation
сA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119334 Moscow, Russian Federation.
The heteronuclear complex [Fe4Li2(O)2(Piv)10(H2O)2] (1, Piv is the pivalic acid anion) was
obtained by refluxing FeIII pivalates with LiI pivalates in toluene and isolated as the 1•PhCH3
solvate with a toluene molecule. According to X-ray diffraction data, complex 1 contains the
{Fe4Li2O2} core. The Mössbauer spectroscopy data indicate that the core comprises paramagnetic
FeIII ions in the high-spin state located in the symmetric octahedral environment of oxygen
atoms. Thermolysis of 1 studied by simultaneous thermal analysis demonstrated thermal stabil-
ity of the complex up to 225 С. The main end product of thermolysis at 600 С is the mixed
oxide LiFe5O8.
Key words: heterometallic pivalate complexes, iron(III), lithium, crystal structure, Mössbauer
spectroscopy, simultaneous thermal analysis.
Heterometallic iron-based pivalate (trimethylacetate)
complexes are of interest from different standpoints: they
serve as components of homo- or heterogeneous catalytic
systems, possess unique magnetic behavior (associated
with the transition to magnetically ordered state at low
temperature), electrical conductivity, sorption capacity,
and other properties.1—7 Furthermore, variation of the
nature of heteroatom M and the Fe : M ratio in these
molecules may provide the use of these compounds in
chemical engineering processes for the production of
various functional materials (e.g., complex oxides).8—10
Oxides of this type with 3d element ions (e.g., LiCoO2 and
LiMn2O4) prepared as films by thermolysis of polynuclear
Li-3d metal heterometallic complexes are known as pro-
mising cathode materials for lithium batteries and other
electric devices.11,12 However, the active search for alter-
native, less toxic, and less expensive cathode materials
carried out in recent years brought to the forefront the
development of optimal approaches to the synthesis of
heterometallic structures with iron(III) and lithium(I) ions,
possible molecular precursors for the synthesis of various
types of oxide materials, which are promising, according
to published data, as electrode components.13—16
It is noteworthy that among the known monocarb-
oxylic acid metal complexes, there is only one molecular
complex containing both iron(III) and lithium(I) ions,
namely, [Fe6Li5(O)2(ButPO3)6(Piv)8(MeOH)2(py)4]
(HPiv is pivalic acid, py is pyridine).17 Meanwhile, a vari-
ety of compounds with different composition and structure
are known for molecular Li—M carboxylate complexes,
where M = Co, Ni, Zn, namely, [Ni5Li6(OH)2(fpo)2(Piv)12-
(HPiv)4] (Hfpo is 5-trifluoromethyl-3-pyrazolin-5-one),18
[Ni2Li2(Piv)6L2] (L is 2,2´-bpy, dimethoxyethane),19
[Co2Li2(O2CR)6L2] (O2CR is Piv, 2-naphthoic acid anion;
L is NEt3, 2,4-lutidine, 2,2´;6´,2´´-terpyridine, 4-thienyl-
substituted pyrimidines),19‒23 and [Zn2Li2(Piv)6(py)2].24
Also, non-crystalline heterometallic compounds of mono-
and dicarboxylic acids can be used for the preparation of
lithium ferrites. 25—30
This paper describes the synthesis, structure, and
properties of a new polynuclear oxo-pivalate complex with
the FeIII and LiI ions.
Results and Discussion
One of the most stable polynuclear structures con-
taining bridging pivalate groups between FeIII ions is
the trinuclear cationic complex [Fe3O(Piv)6L3]+ (where
L = H2O, py, etc.),20,31 which is used as the starting com-
* Dedicated to Academician of the Russian Academy of Sciences
I. P. Beletskaya.
† Deceased.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0449—0454, March, 2018.
1066-5285/18/6703-0449 © 2018 Springer Science+Business Media, Inc.

450
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 3, March, 2018
Lutsenko et al.
pound for the preparation of heteronuclear molecules
including various coordination polymers.30—34 These
compounds are of most interest, because they extend the
range of geometric and elecronic characteristics of the
final architecture via introduction of various metal ions or
metal-organic groups with different electronic and spatial
characteristics into the metal core. Examples of this type
of transformations and final molecules are heteronuclear
complexes containing MnII, MnIII, or ZnII ions, apart
from FeIII ions.35,36
Table 1. Selected bond lengths, interatomic distances (d) in
complex 1•PhCH3
Bond
d/Å
Bond
d/Å
М—О(4-О)
Fe(1)—O(1M)
Fe(2)—O(1M)
Fe(3)—O(1M)
Fe(2)—O(2M)
1.868(2)
1.956(2)
1.973(2)
1.980(2)
Fe(3)—O(2M) 1.943(2)
Fe(4)—O(2M) 1.865(2)
Li(1)—O(2M) 1.990(6)
Li(2)—O(1M) 1.981(5)
М—О(Piv)
We found that the reaction of [Fe3O(Piv)6(H2O)3]∙Piv–
with Li(Piv) (Fe : Li = 2 : 1) in toluene at 110 С gives
rise to the crystals of [Fe4Li2(O)2(Piv)10(H2O)2] solvated
with a toluene molecule (1·PhCH3). The complex
1•PhCH3 crystallizes in the monoclinic system, space
group P21/c. The metal core of the complex is the
{Fe4Li2O2} (Fig. 1) group composed of two Fe3Li tetra-
hedra sharing the Fe(2)Fe(3) face. In each Fe3Li tetra-
hedron, metal ions are bridged by the 4-oxo group (selected
bond lengths and angles are summarized in Tables 1
and 2). The metal atoms are additionally linked by six
O,O´-2-, two O,O-2-, and two O,O,O´-3-carboxylate
bridges. Formally, the {Fe4Li2O2} metal core in 1 resem-
bles the known {M´2M´´4O2} core in the hexanuclear
transition metal complexes [M´2M´´4(O)2(O2CR)10L4]
(M´ = FeIII, MnIII; M´´ = MnII, FeII,CoII, NiII).37—39
The coordination environment of the iron central at-
oms, FeO6, is an octahedron, like those of the peripheral
Fe(1) and Fe(4) atoms, which coordinate additionally one
water molecule each (Fig. 1). The lithium environment,
LiO4, is a distorted tetrahedron, with the metal atoms
Fe(1)—O(1)
Fe(1)—O(3)
Fe(1)—O(5)
Fe(1)—O(17)
Fe(2)—O(2)
Fe(2)—O(4)
Fe(2)—O(7)
Fe(2)—O(9)
Fe(3)—O(6)
Fe(3)—O(11)
Fe(3)—O(13)
2.028(2)
1.988(2)
2.002(2)
2.145(2)
2.008(2)
2.020(2)
2.009(2)
2.063(2)
2.010(2)
2.022(2)
2.016(2)
Fe(3)—O(19)
Fe(4)—O(8)
Fe(4)—O(12)
Fe(4)—O(14)
Fe(4)—O(15)
Li(1)—O(15)
Li(1)—O(20)
Li(1)—O(9)
Li(2)—O(10)
Li(2)—O(17)
Li(2)—O(19)
2.058(2)
1.989(2)
2.024(2)
2.005(2)
2.151(2)
1.974(6)
1.909(6)
1.989(6)
1.890(6)
1.989(6)
2.003(6)
M—О(H2O)
2.083(2) Fe(4)—O(2W) 2.084(2)
M…M´
Fe(1)—O(1W)
Fe(1)…Fe(2)
Fe(2)…Fe(3)
Fe(3)…Fe(4)
Fe(1)…Fe(4)
Fe(1)…Li(2)
Fe(4)…Li(1)
3.3475(6)
2.9604(6)
3.3368(3)
5.8739(4)
2.920(5)1
5.937(4)1
Fe(2)…Li(1)
Fe(2)…Li(2)
Fe(3)…Li(1)
Fe(3)…Li(2)
Fe(4)…Li(1)
Li(1)…Li(2)
2.936(5)
3.250(5)
3.236(5)
2.940(5)
2.938(5)
3.931(6)
O(10)
O(2)
O(9)
Li(1)
O(1)
Fe(2)
O(15)
O(20)
O(7)
Li(2)
O(17)
O(16)
O(8)
O(1M)
O(18)
O(19)
Fe(1)
Fe(4)
O(2M)
O(4)
Fe(3)
O(1W)
O(3)
O(2W)
O(12)
O(5)
O(11)
O(14)
O(6)
O(13)
Fig. 1. Molecular structure of complex 1 (Н atoms and methyl groups are not shown).

Pivalate complex with Li and FeIII ions
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 3, March, 2018
451
Table 2. Selected bond angles () in complex
1•PhCH3
atoms of the O,O-2-carboxylate bridges. The H-bonding
of neighboring molecules of the complex gives rise to a
supramolecular chain (Fig. 3).
Angle
/deg
According to powder X-ray diffraction data, the single-
phase polycrystalline precipitate isolated from the reaction
mixture was identified as complex 1•PhCH3 (Fig. 4).
The oxidation states and the spin state of the iron ions
in complex 1•PhCH3 were studied by Mössbauer spec-
troscopy. The Mössbauer spectrum of 1•PhCH3 recorded
at room temperature in a zero magnetic field is a single
doublet (Fig. 5). The Mössbauer isomer shifts () and
quadrupole splittings () attest to the presence of only
high-spin iron(III) ions in the octahedral oxygen environ-
ment, which is consistent with X-ray diffraction data. The
isomer shifts and quadrupole splittings in the ranges of
0.36—0.43 mm s–1 (for ) and 0.75—0.85 mm s–1 (for )
are comparable with the data measured previously for
heterometallic {FeIII—MII} complexes (MII = Mn, Co,
Zn).10,35,36
Fe(1)—O(1M)—Fe(2)
Fe(1)—O(1M)—Fe(3)
Fe(2)—O(1M)—Fe(3)
Fe(2)—O(2M)—Fe(3)
Fe(2)—O(2M)—Fe(4)
Fe(3)—O(2M)—Fe(4)
Fe(1)—O(1M)—Li(2)
Fe(2)—O(1M)—Li(2)
Fe(3)—O(1M)—Li(2)
Fe(2)—O(2M)—Li(1)
Fe(3)—O(2M)—Li(1)
Fe(4)—O(2M)—Li(1)
122.21(10)
127.59(10)
97.79(8)
97.98(8)
127.48(10)
122.44(10)
98.7(2)
111.3(2)
96.1(2)
95.4(2)
110.7(2)
99.3(2)
It seemed pertinent to study the thermal behavior of
complex 1•PhCH3 and to determine the temperature of
its decomposition to oxides and products of thermolysis.
The thermal behavior of 1 was investigated by simultane-
ous thermal analysis (STA) in an argon atmosphere with
recording of both TG and DSC curves (Fig. 6). Analysis
of the TG curve (see Fig. 6,a) shows that complex
1•PhCH3 is thermally stable up to 225 C (a minor endo-
them at 59 C (see Fig. 6, b) corresponds to the partial
removal of the toluene molecule mcalc/exp (%) = 6.5/4.3).
Generally, the complex does not undergo any changes
below 225 C.
In the temperature range of 271—360 C, destruction
and subsequent decomposition of the organic part of the
complex take place. The previously studied thermolysis
processes and the gas phase composition for pivalate sys-
tems indicate that a variety of low-molecular-weight
carbon products (СH2O, C4H8, C5H10O, etc.) are formed
in the 270—370 C range.36,40,41 In this temperature range,
Li(2)
Fe(2)
Li(1)
Fe(4)
Fe(1)
Fe(3)
Fig. 2. FeO6 and LiO4 polyhedra in complex 1.
being located close to the plane formed by the carboxylate
oxygen atoms (the Li deviation from the O3 plane is
0.092(6) and 0.094(5) Å for Li(1) and Li(2), respectively)
(Fig. 2).
In the crystal, intermolecular H-bonds (O…O 2.772 Å)
occur between the hydrogen atoms of the coordinated
water molecules and the metal-uncoordinated oxygen
Fig. 3. Fragment of the molecular packing of complex 1 in the crystal; the dashed lines designate the intermolecular H-bonds (Н
atoms are not shown).

452
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 3, March, 2018
Lutsenko et al.
I/pulse
7000
6000
5000
4000
3000
2000
1000
0
1
2
a
b
30
40
50
60
70
80
2/deg
Fig. 7. Powder X-ray diffraction pattern of the product of ther-
molysis of complex 1•PhCH3 at 600 C in an inert atmosphere
(dots), simulated X-ray diffraction pattern (a), and their differ-
ence (b). (The central vertical line reflects the position of the
substrate peak)
5
10
15 20
25
30 35
40 2/deg
Fig. 4. Comparison of the experimental (1) and theoretical (2)
powder X-ray diffraction patterns of complex 1•PhCH3.
of the residual weight of the thermolysis product and
powder X-ray diffraction data (Fig. 7) suggests that the
complex oxide LiFe5O8 is formed as the main thermal
decomposition product (mcalc/exp = 29/30%).43
A (rel. units )
1.000
0.995
Thus, we demonstrated that the reaction of [Fe3O-
(Piv)6(H2O)3]•Piv with Li(Piv) (2 : 1) gives the polynu-
clear Fe—Li complex [Fe4Li2(O)2(Piv)10(H2O)2]•PhCH3
(1). It is known that in the presence of divalent d-metal
ions, the manganese(III) and iron(III) atoms form hexa-
nuclear homo- or heteronuclear complexes
[M´2M´´4(O)2(O2CR)10L4] (M´ = FeIII, MnIII); M´´ =
= MnII, FeII, CoII, NiII). In this case, the replacement of
doubly charged d-metal ion by a singly charged LiI ion in
the reaction with iron pivalate results in the generation of
a new complex with a similar geometry of the hexanuclear
metal core. According to the Mössbauer spectroscopy data,
all iron ions in complex 1 are in the high-spin state. The
results of thermal analysis demonstrated stability of the
complex up to 225 C. The final product of thermolysis at
600 C is the mixed oxide LiFe5O8.
0.990
0.985
–10
–5
0
5
/mm s–1
Fig. 5. Mössbauer spectrum of 1•PhCH3 (solid sample, Т = 300 K).
Q/mW mg–1
m (%)
–4.34 %
a
b
1
100
50
0
336 С
32.5 %
0
59 С
277 С
311 С
–1
50 100 150 200 250 300 350 400 T/С
Fig. 6. TG (а) and DSC (b) curves for complex 1•PhCH3.
Experimental
endothermic effects (peaks at 277, 311, and 336 C) are
observed for this complex, corresponding to successive
decomposition of the carboxylate anions. However, ther-
molysis up to 450 C did not lead to stabilization of the
weight as was the case, for example, for decomposition
of the molecular complexes [Ni2Li2(Piv)6(2,2´-bpy)2],
[Co2Li2(Piv)6L2] (L is NEt3, 2,4-lutidine, 2-amino-5-
methylpyridine), and [Fe2Zn4O2(Piv)10])19,22,36,42. The
supplementary experiment (in a corundum crucible) was
performed to find out that the final temperature where all
thermal destruction processes are completed is 600 C,
with the overall weight loss being 70%. Thus, comparison
The complexes were synthesized from commercial reagents
and solvents, which were used as received: pivalic acid (99%,
Merck), LiOH (analytical grade), and toluene (special purity
grade, Khimmed). The complex [Fe3O(Piv)6(H2O)3]•Piv was
prepared by a known procedure.31 Lithium pivalate, Li(Piv), was
prepared by the reaction between equimolar amounts of LiOH
and HPiv in aqueous solutions followed by evaporation; the
solid phase thus formed was washed with hexane.
IR spectrum was measured on a Perkin—Elmer Spectrum 65
Fourier Transform spectrophotometer in the attenuated total
reflectance (ATR) mode in the frequency range of 400—
4000 cm–1
.

Pivalate complex with Li and FeIII ions
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 3, March, 2018
453
Elemental analysis was carried out on a Carlo Erba EA 1108
automatic С,H,N,S-analyzer; metals were quantified by induc-
tively coupled plasma mass spectrometry (ICP-MS) (Agilent
7500ce; Agilent Technologies Inc., USA).
Powder X-ray diffraction analysis was carried out on a Bruker
D8 Advance diffractometer (LynxEye detector, Ge(III) mono-
chromator, (Cu-K1) = 1.54060 Å).
and differential scanning calorimetry (DSC) curves. The STA
was performed using an STA 449 F1 Jupiter (NETZSCH) instru-
ment and aluminum crucibles covered with a lid containing a
hole to maintain the vapor pressure of 1 atm during the thermal
decomposition. Heating to 450 C at a rate of 5 C min–1 was
used. The sample weight was 0.61 mg. The accuracy of tempera-
ture measurement was 0.7 C, the weight changes were deter-
mined to an accuracy of 1•102 mg. While recording the TG
and DSC curves, a correction file and temperature and sensitiv-
ity calibrations at a specified temperature program and heating
rate were used.
Bis(µ3-oxo)bis(µ2-trimethylacetato-О,О)bis(µ3-trimethyl-
acetato-О,О,О´)hexakis(µ2-trimethylacetato-О,О´)bis-(µ´-aquo)-
dilithiumtetrairon(III), toluene solvate, [Fe4Li2(O)2(Piv)10
-
(H2O)2]•PhCH3 (1•PhCH3). Weighed portions of [Fe3O-
(Piv)6(H2O)3]•HPiv (100 mg, 0.11 mmol) and Li(Piv) (17 mg,
0.16 mmol) were dissolved in toluene with heating and refluxed
(110 C) for 1 h. The solution thus formed was slowly cooled to
room temperature and kept for 24 h. The light brown crystals
that precipitated after 24 h were separated from the mother liquor
by decantation and dried in air. The yield of [1•PhCH3] was
70 mg (63% in relation to the initial iron complex). According
to ICP MS data (mg mL–1): Fe : Li = 0.19 : 0.08. Found (%):
C, 48.83; H, 7.54. Fe4Li2O24C57H102. Calculated (%): C, 48.60;
H, 7.30. IR, /cm–1: 2969 m, 2931 w, 2873 w, 1626 m, 1569 vs,
1534 br.s, 1481 s, 1422 s, 1378 w, 1360 s, 1346 s, 1219 vs, 1085 vw,
1031 w, 938 w, 872 w, 789 m, 733 m, 696 w, 643 w, 598 s, 554 w,
514 m, 459 vs, 419 br.m, 436 br.m.
This work was financially supported by the Russian
Science Foundation (Project No. 14-23-00176P).
X-ray diffraction, simultaneous thermal, and elemen-
tal analyses were carried out using the equipment of the
Center for Collective Use of the N. S. Kurnakov Institute
of General and Inorganic Chemistry. Powder X-ray dif-
fraction analysis was performed using the equipment of
the Molecular Structure Research Center of the A. N.
Nesmeyanov Institute of Organoelement Compounds.
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data and structure refinement details for the complex 1•PhCH3
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=
= 1408.67 g mol–1, the crystals are brown parallelepipeds, space
group P21/с, a = 15.1440(12) Å, b = 22.586(2) Å, c = 21.335(2) Å,
 = 94.683(2), V = 7273.0(10) Å3, Z = 4, ρcalc = 1.286 g cm–3
,
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Received January 15, 2018;
in revised form January 26, 2018;
accepted January 29, 2018