ARTICLE
DOI: 10.1002/zaac.201300172
Proton NMR Investigations of Intermediate Spin Iron(III) Complexes with
Macrocyclic N42– Chelate Ligands
Birgit Weber,*[a] F. Ann Walker,[b] and Konstantin Karaghiosoff[c]
Keywords: Iron; Macrocycles; NMR spectroscopy; X-ray diffraction; Intermediate-spin
Abstract. Proton NMR spectra of five macrocyclic iron(III) intermedi-
ate-spin complexes are investigated. The signal assignment was ac-
complished for all five complexes. The temperature dependence of the
NMR spectra reveals that for complexes of the type Fe1 an ideal Curie
behaviour is observed indicating the absence of excited states. This is
Introduction
Solution NMR spectroscopy is a valuable tool for studying
paramagnetic complexes because the unpaired electron causes
paramagnetic (isotropic) shifts of the protons of the equatorial
(and axial) ligands. The magnitude of the shift of the proton is
dependent on the position of the proton with respect to the
paramagnetic centre and the electron configuration.[1a] This re-
sulted in the application of this technique to paramagnetic mo-
lecules and biomolecules for more than 40 years. It was shown
to be an useful and sensitive method for detecting changes
in the electronic ground state (including spin transitions[2]) in
transition metal complexes and there are plenty of textbooks
and reviews dealing with this topic.[1] Here we present 1H
NMR spectra of a series of pentacoordinate iron(III) com-
plexes with macrocyclic N42– ligands. Ligands of this type
were first synthesised by Jäger et al. and are frequently known
as Jäger-ligands.[3–5] They show a high potential as structural
and/or functional models of active sites of metalloenzymes.
The tetradentate twofold negatively charged macrocyclic li-
gands with a [N4] donor set and a more or less extended π-
system are closely related to the porphyrins.[4] Thus the ques-
tion arises what information can be obtained from the NMR
spectra of those complexes.
* Prof. Dr. B. Weber
Fax: +49-921-552157
E-Mail: weber@uni-bayreuth.de
[a] Inorganic Chemistry II
Universität Bayreuth
Universitätsstr. 30
95440 Bayreuth, Germany
[b] Department of Chemistry
The University of Arizona
Tucson, AZ, 85721–0041, USA
[c] Department of Chemistry
Ludwig-Maximilians-Universität München
Butenandtstraße 5–13
81377 Munich, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201300172 or from the au-
thor.
1498 © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
not the case for complexes of the type Fe2 and Fe3. A significant
deviation from the Curie straight line is observed for Fe3-Cl indicating
low-lying excited states. Single crystals suitable for X-ray structure
analysis were obtained for the complexes Fe2-Cl and Fe3-I and the
X-ray structure of those two complexes is presented.
According to literature, 1H NMR spectra of intermediate-
spin iron(III) complexes are easier to interpret than the ones
for the low-spin or high-spin state. This is because for the
intermediate-spin state the dipolar (through space) contribution
to the paramagnetic shift is relatively small and the observed
shift can be described with help of the contact term given in
equation (1) if a single spin state with an isotropic g-tensor is
populated.[1a]
QρC ⬍g⬎βS(S+1)
δcon = (1)
2S 3γNRkT
The first term (QρC/2S) is the hyperfine coupling constant.
Here Q is a constant for the type of proton which is observed.
It is negative if the delocalisation of the spin occurs through a
conjugated π-system to the carbon atom to which the proton
in question is attached. If the spin delocalisation to the carbon
atom occurs through σ bonds it is positive. ρc is the unpaired
electron density at the carbon to which the proton is attached,
⬍g⬎ the isotropic g-value and S the total spin of the system
under investigation.[1a]
Consequently we decided to investigate the proton NMR
spectra of the iron(III) intermediate-spin (S = 3/2) complexes
that are obtained if chloride or iodide [3,6] serve as axial ligand.
The basic formula of the complexes and the numbering scheme
used for the assignment of the NMR signals are given in
Scheme 1.
Results and Discussion
1
H NMR Spectroscopy – Signal Assignment
Proton NMR spectra of the complexes Fe1-Cl, Fe1-I,
Fe2-Cl, Fe3-Cl and Fe3-I in [D8]toluene were investigated in
the 95 to –70 °C temperature range. In the Supporting Infor-
mation, Tables S1–S5, the tabulated resonances for all five
complexes with the signal assignment is given. In Figure 1 the
Z. Anorg. Allg. Chem. 2013, 639, (8-9), 1498–1503
Intermediate Spin Iron(III) Complexes with Macrocyclic N42– Chelate Ligands
Scheme 1. Basic structure of the macrocyclic complexes discussed in
this work with X = Cl or I. The numbering schema used for the assign-
ment of the proton NMR resonances is given.
proton NMR spectra of the three chloride complexes Fe1-Cl,
Fe2-Cl and Fe3-Cl are compared. With help of predictions
about the signal shifts based on equation (1) and the signal
intensities a clear assignment is possible for the complex
Fe1-Cl given at the top of Figure 1. In total, resonances for 13
protons were detected in the –200 to 100 ppm region of the
spectrum. This is in excellent agreement with the total of 26
protons present in this complex, if a mirror plane is considered.
Integration of the resonances yields two CH3 groups, one CH2
group and five protons, of which four are close together in the
55–75 ppm region.
Figure 1. 1H NMR spectra of (from up to down) Fe1-Cl (45 °C, A),
Fe2-Cl (95 °C, B) and Fe3-Cl (35 °C, C). The resonance assignment
is as given in Scheme 1. S denotes to the used solvent toluene.
A complete signal assignment can be accomplished by tak-
ing equation (1) into consideration assuming that the dipolar
contribution to the isotropic shift can be neglected and no ex-
cited states are populated. Thus only the constant Q and the
unpaired electron density ρc at the carbon atoms need to be
considered.[1a] The carbon atoms of the two CH3 groups are
both bound through σ-bonds to the macrocycle; the only differ-
ence is the number of bonds between the proton and the para-
magnetic centre that is higher for the ester group. Thus this
carbon atom has a lower unpaired electron density and the
Z. Anorg. Allg. Chem. 2013, 1498–1503 © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
proton resonances appear closer to the diamagnetic region. The
signal at 2 ppm can be assigned to CH3 (1) and the signal
around 55 ppm belongs to the CH3 group (3). The CH2 group
of the ethyl ester (2) is observed around 13 ppm – closer to
the diamagnetic region than all the other resonances. Of the
remaining five signals, each with the intensity of one, one ap-
pears with a strong higher shielded signal around –180 ppm.
This is the only highly shielded signal indicating an opposite
sign of the constant Q. The only proton attached to a carbon
atom involved in the π-system of the ligand is proton (4) which
is assigned to the highly shielded resonance. The other four
resonances at around 60 ppm of an intensity of 1 are assigned
to the four protons of the two ethylene bridges. On the first
view only two resonances with an intensity of two would be
expected, or even only one resonance with a relative intensity
of 4. The reason for the further splitting is the rigid nature of
the ethylene bridge that results in different conformations of
the single protons with regard to the paramagnetic centre (see
X-ray structure in Figure 6). Such differences result in dif-
ferent contributions to the contact shifts that are responsible
for the splitting of the signal.
Substitution of one ethylene bridge in Fe1-Cl by a phenyl-
ene bridge (Fe2-Cl, Figure 1B) leads to the disappearance of
two of the ethylene bridge signals (H5) and a new signal
around –10 ppm is observed that can be assigned to a proton
of the phenylene bridge (H6 or H7). The signal for the second
phenylene proton is probably in the diamagnetic region of the
spectrum and difficult to detect. A similar observation was
made for the 1H NMR spectra of high-spin iron(II) complexes
of the same ligand family.[2a] The higher shielding of this new
resonance is in agreement with the participation of the corre-
sponding carbon atom in the π-system of the ligand.
Further replacement of an ethylene bridge by a phenylene
bridge (Fe3-Cl, Figure 1C) leads to drastic changes in the
spectrum. As expected, additional signals with negative chemi-
cal shifts can be observed and the signals of the protons of the
ethylene bridge (H5) disappear completely. Additionally, the
magnitude of the paramagnetic shifts is small compared to
those of Fe1-Cl and Fe2-Cl and further changes for the known
signals are observed. The signal of the protons of the CH2
group is split into two because they are diastereotopic. This
could be expected for Fe1-Cl and Fe2-Cl as well, but those
two complexes have a more flexible ligand so the splitting will
be too small to be observed. Another remarkable difference is
the position of the resonance of the methyl group (3), which
is shifted to the high-field region of the NMR spectrum. This
clearly indicates that either significant contributions from the
dipolar shift to the isotropic shift are observed or an excited
spin state (1–3 kT above the ground state) influences the para-
magnetic shift. A possible excited state would be the S = 5/2
high-spin state for this type of complexes. Indeed, the ligand
field strength decreases from Fe1 to Fe3 thus the probability
for the observation of the high-spin state increases.[3,7] In the
Supporting Information, Figure S1, the magnetic measure-
ments of the three complexes up to 350 K are given. In all
cases the complexes clearly remain in the S = 3/2 intermediate-
spin state in the whole temperature range investigated with a
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ARTICLE B. Weber, F. A. Walker, K. Karaghiosoff

room temperature magnetic moment in the region of

2 cm3·K·mol–1. No indication for a starting spin transition in
the case of Fe3-Cl is observed.[3]

1
H NMR Spectroscopy – Temperature Dependence

The temperature dependence of the proton NMR shifts can

give further information about the ground state and possible
electronic excited states of the compound under investigation.
If the excited states are energetically well separated from the
ground state, Curie behaviour is observed. With increasing
temperatures the isotropic shift decreases and the resonances
shift towards the diamagnetic region of the spectrum. The plot
of the isotropic shift vs. 1/T gives a straight line through the
origin.
In Figure 2 the temperature dependent 1H NMR spectra of
Fe1-I in toluene are given. The spectra are very similar to
those of Fe1-Cl with all signals slightly shifted. This is due to
small differences in the unpaired electron distribution of the
complexes that is also reflected in different g-tensors (gy =
5.38, gx = 2.70, gz = 1.74 for Fe1-I[6] and gy = 4.59; gx = 3.49;
gz = 2.04 for Fe1-Cl[3]). It can be clearly seen, that at higher
temperatures the resonances shift towards the diamagnetic re-
gion. Especially for the aromatic proton 4 the shift is very
pronounced, from –189 ppm at 25 °C to –150 ppm at 95 °C.
Figure 3. Isotropic shift of the 1H NMR signals of Fe1-Cl and Fe1-I
plotted against 1/T (dots). An ideal Curie behaviour is observed for
both complexes (solid line).

Figure 3 shows the isotropic shifts plotted against 1/T for

Figure 2. Temperature dependence of the 1H NMR signals of Fe1-I.
The resonance assignment is as given in Scheme 1. S denotes to the
used solvent toluene.
Fe1-Cl and Fe1-I. An ideal Curie behaviour is observed in
both cases. There are no indications for low-lying excited
states that would influence the proton NMR spectra. This is in
agreement with calculations performed for both complexes that
show that the S = 3/2 ground state is well separated from the
S = 5/2 excited state for both complexes.[3,6]
In Figure 4 the temperature dependence of the 1H NMR
spectra of Fe3-Cl is given. In this case the temperature depen-
dence of the observed shifts no longer obeys the Curie law. In
Figure 5 the plot of the observed shift vs. 1/T is compared for
Fe3-Cl and Fe3-I.
As can be seen from Figure 5, the temperature dependence
of the observed shift of Fe3-I is almost linear in the investi-
gated temperature region. In contrast to this for Fe3Cl a strong
curvature for some of the resonances is observed. Several pos-
sible reasons may be responsible for this deviation. Among
those, hindered rotation e.g. of the ethyl groups, large dipolar
shifts due to a large magnetic anisotropy (zero-field splitting)
of the iron centre or thermally-accessible excited states are
three obvious possibilities. If the dipolar shift were large, then
it should show a D/T2 dependence, where D is the zero-field
splitting constant. A D/T2 dependence in addition to a C/T de-
pendence is not what is observed here. Hindered ethyl group
rotation could contribute to the curvature, but the ethoxy
groups should not exhibit hindered rotation because of the ad-
ditional single bond that removes the ethyl group from the

1500 www.zaac.wiley-vch.de © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Z. Anorg. Allg. Chem. 2013, 1498–1503
Intermediate Spin Iron(III) Complexes with Macrocyclic N42– Chelate Ligands
congestion of the macrocycle. Additionally, for the first two
possibilities deviations from the Curie law would have been
also observed for the other complexes. Instead, the most likely
reason for curvature of the Curie plots is a thermally-accessible
excited state. The experimental data in Figure 5 (dots) were fit
by taking an extended Curie law into account with different
Curie constants (or spin densities) for the ground and excited
states:
δcon
n = (F/T){W1C2n1 + W2C2n2e–ΔE/kT} / {W1+W2e–ΔE/kT}
where W1 and W2 are the weighting factors for the ground
and excited state (S(S+1) in each case), Cn1 and Cn2 are the
orbital coefficients (spin densities) for ground state and excited
state, F is the Curie constant, ΔE is the energy difference be-
tween the ground state and the first excited state and k is the
Boltzman constant. The most likely excited state is the corre-
sponding high-spin state where a total spin of S = 5/2 is ob-
served. Thus the experimental data of Fe2-Cl, Fe3-Cl and
Fe3-I were fit following this assumption, however, other pos-
sible spin states were tried and shown not to produce reliable
fits. The fit obtained with the TDF (temperature dependent
Figure 4. Temperature dependence of the 1H NMR signals of Fe3-Cl.
The resonance assignment is as given in Scheme 1. S denotes to the
used solvent toluene.
Figure 5. Observed shift of the 1H NMR signals of Fe3-Cl (A) and Fe3-I (B) plotted against 1/T. In both cases a strong deviation from the
ideal Curie law is observed indicated by the curvature of the lines that is more pronounced for Fe3-Cl. The solid line represents the fit of the
data with parameters and model described in the text.
Z. Anorg. Allg. Chem. 2013, 1498–1503 © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
fitting) program written by Shokirev and Walker[8] (solid lines)
simulates the temperature dependence of the isotropic shift of
Fe3-Cl and Fe3-I very well. In the case of Fe2-Cl (Supporting
Information, Figure S2) no reasonable results were obtained.
The best-fit parameters are given in Table 1. The ΔE obtained
for Fe3-Cl is with 80 cm–1 in 1–3 kT region. Thus, although
no indication for a starting spin transition is observed in the
magnetic measurements up to 350 K, with the help of tempera-
ture dependent NMR spectroscopy a low-lying excited high-
(2)
spin state could be identified. For Fe3-I and Fe2-Cl signifi-
cantly higher energy differences are obtained. Thus the ligand
field strength of these complexes is influenced by both the
equatorial and the axial ligand. The outcome of those tempera-
ture dependent NMR experiments is very interesting with re-
gard to the properties of related iron(III)-halide complexes of
this general type. Pentacoordinated halides of iron porphyrins
are high-spin compounds as is the complex Fe(Me4TAA)Cl[9]
(where M4TAA is tetramethyldibenzotetraaza[14]annulene).
This complex is closely related to Fe3-Cl with protons instead
of the ester groups (at C2 and C11 in Figure 6) and four methyl
substituents instead of two (at C1, C3, C10 and C12 in Fig-
ure 6). The difference in the electronic ground state were dis-
cussed to be due to a stronger “saddle shaped” ligand in the
case of Fe(Me4TAA)Cl because of the steric strain induced by
the four methyl substituents.[9]
Table 1. Summary of results obtained from the TDFw[12] Fits of the
temperature dependence of the assigned protons for the complexes in
this study.
System E1 (GS) E2 (ES) ΔE12 [cm–1] MSD
Fe2-Cl 3/2 5/2 1892 0.273
Fe3-Cl 3/2 5/2 80 0.328
Fe3-I 3/2 5/2 645 0.106
X-ray Structure Analysis
Crystals suitable for X-ray structure analysis were obtained
for Fe2-Cl and Fe3-I by slow recrystallization of the complex
from toluene. In Figure 6 the molecular structure of the two
complexes is given together with the already published struc-
ture of Fe1-Cl[3] for comparison purpose. In Table 2 selected
bond lengths and angles within the inner coordination sphere
are summarized. In Table 3 the crystallographic data are given.
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ARTICLE B. Weber, F. A. Walker, K. Karaghiosoff

Table 2. Selected bond lengths /Å and angles /° of Fe1-Cl,[3] Fe1-I,[6] Fe2-Cl and Fe3-I.
Fe–N Fe–X N–Fe–N Fe–N4
Fe1-Cl 1.909(5), 1.920(5), 1.912(5), 1.948(5) 2.262(4) 0.41
Fe1-I 1.892(3), 1.884(3), 1.925(3), 1.924(3) 2.637(1) 0.34
Fe2-Cl 1.906(2), 1.907(2), 1.925(2), 1.937(2) 2.288(1) 83.6(1), 91.0(1), 91.1(1), 86.2(1) 0.36
Fe3-I 1.894(4), 1.912(4), 1.933(4), 1.948(4) 2.670(1) 82.8(2), 90.9(2), 91.2(2), 84.3(2) 0.42

Table 3. Crystallographic data for Fe2-Cl and Fe3-I.

Fe2-Cl Fe3-I
net formula C22H26ClFeN4O4 C26H26IFeN4O4
Mr/g mol–1 501.77 641.259
crystal size/mm 0.09 ⫻ 0.03 ⫻ 0.01 0.37 ⫻ 0.12 ⫻ 0.08
T/K 200(2) 200(2)
radiation MoKα MoKα
diffractometer Nonius KappaCCD Nonius KappaCCD
crystal system monoclinic triclinic
space group P21/n P1̄
a /Å 8.1200(2) 7.5470(10)
b /Å 13.6360(3) 12.411(2)
c /Å 19.9840(4) 14.475(2)
α /° 90 79.437(11)
β /° 96.6750(10) 82.654(11)
γ /° 90 73.186(12)
V /Å3 2197.72(8) 1271.8(3)
Z 4 2
calcd. density /g cm–3 1.515 1.675
μ /mm–1 0.845 1.847
absorption correction none numerical
refls. measured 9376 7476
Rint 0.0307 0.063
θ range 3.16– 27.52 4.19– 27.56
x, y (weighting scheme) 0.04870, 1.07940 0.08270, 0
hydrogen refinement constrained constrained
Indep. reflections 5040 5774
parameters 300 340
restraints 0 0
R(Fobs) 0.0426 0.0497
Rw(F2) 0.1077 0.1327
S 1.010 0.983
max electron density /e Å–3 0.499 1.572
min electron density /e Å–3 –0.386 –1.297

Figure 6. ORTEP drawing of the molecule structure of Fe1-Cl,[3]

Fe2-Cl and Fe3-I. the phenyl ring is significantly bent out of the plane deter-
mined by the four nitrogen atoms with an angle of 21.5°. In
As for the previously published halide complexes Fe1-Cl contrast to this, for the second phenyl ring only an angel of
and Fe1-I of this ligand type,[3] the iron centre of Fe2-Cl and 3.0° is observed. This structure clearly illustrates the influence
Fe3-I is in a square-pyramidal coordination sphere. The of the methyl groups on the saddle shape of the macrocyclic
average Fe–Neq bond lengths are with 1.90–1.93 Å in the same ligand from Fe3. Those steric interactions could be responsible
order of magnitude as observed for other low-spin or interme- for the shift of the methyl group resonance to higher fields in
diate-spin complexes of this ligand type.[3–5] They are signifi- the NMR spectrum.
cantly shorter than the bond lengths of closely related por-
phyrin complexes that are in the range of 2.0 Å. This is due to
the different chelate ring sizes of the two ligand systems. The
bond length to the axial ligand strongly depends on the axial
ligand and is significantly longer for the iodide complex. In
contrast to this, no correlation can be found for the distortion
of the iron centre from the equatorial N4 plane. From the data
in Table 2 it appears to depend on the interplay of the equato-
rial and the axial ligand. In Figure 7 a side-view of Fe3-Cl is Figure 7. Side-view of the structure of Fe3-I to illustrate the influence
given to illustrate the influence of the methyl groups on the of the sterically demanding methyl groups (circle) on the distortion of
saddle-shape of the ligand. On the side of the methyl groups the ligand from planarity.

1502 www.zaac.wiley-vch.de © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Z. Anorg. Allg. Chem. 2013, 1498–1503
Intermediate Spin Iron(III) Complexes with Macrocyclic N42– Chelate Ligands
Conclusions
The proton NMR spectra of five iron(III) intermediate spin
complexes were presented. The signal assignment was ac-
complished for all complexes by following the predictions
based on Equation (1) (Fe1-Cl, Fe1-I and Fe2-Cl) and by
spectral comparison. The temperature dependence of the iso-
tropic shifts revealed, that for Fe1-Cl, Fe1-I, and to some ex-
tent also for Fe2-Cl, an ideal Curie behaviour of the isotropic
shifts is observed. This is in agreement with the outcome of
DFT calculations which show, that the intermediate-spin state
is energetically well separated from the high-spin excited
state.[3,6] For the two complexes of Fe3 a deviation from the
Curie law is observed that is especially pronounced for the
chloride complex. This is due to an energetically low-lying
excited high-spin state in the 1–3 kT region. The NMR spectra
confirm the decrease of the ligand field strength from Fe1 to
Fe3 that leads to a stabilisation of the excited high-spin state.
This example demonstrated that by interpretation of the solu-
tion NMR spectra of paramagnetic complexes further infor-
mation can be obtained compared to susceptibility measure-
ments in the solid state or in solution using Evans Method.
The X-ray structures of Fe2-Cl and Fe3-I were solved and
the series for the halide complexes from Fe1 to Fe3 is com-
pleted. The structure of Fe3-I reveals an interesting insight
into the steric strain induced by the interaction from the methyl
groups and the phenyl ring that leads to a saddle shape of
the equatorial ligand of Fe3, that is not so pronounced as for
Fe(Me4TAA)Cl with four methyl groups.
Experimental Section
The synthesis of the complexes was described previously.[3,6]
Preparation of Samples for NMR Measurements: In a Schlenk-flask
(10 mL) the iron(III) halide complex was mixed with deuterated tolu-
ene (1 mL). After stirring for two hours, the samples were transferred
into NMR tubes under an atmosphere of argon and sealed.
The NMR spectra of the toluene solution samples were recorded on a
Varian Unity-300 spectrometer operating at 299.955 MHz equipped
with a Varian variable-temperature unit over the temperature range –70
to + 60 °C. In the high temperature region the NMR spectra were also
recorded on a JEOL EX 400e spectrometer operating at 400.182 MHz
equipped with a variable-temperature unit over the temperature range
+ 25 to + 85 °C. The resonances were referenced by the resonance
from residual solvent protons (δ =2.3 ppm relative to TMS). The tem-
perature was calibrated using the standard Wilmad methanol and ethyl-
ene glycol samples.
Crystal Structure Determination and Refinement: Crystals suitable
for X-ray crystallography were selected by means of a polarization
microscope, mounted on the tip of a glass fiber and investigated on a
Nonius KappaCCD or an Oxford XCalibur 3 diffractometer (Mo-Kα
radiation, λ = 0.71073 Å). The structures were solved by direct meth-
ods – SHELXS-97[10] – and refined by full-matrix least-squares calcu-
lations on F2 with SHELXL-97.[10,11] Anisotropic displacement pa-
rameters were refined for all non-hydrogen atoms. Molecular diagrams
were prepared with ORTEP-III.[12] Intermolecular contacts were ana-
lyzed with Platon[13] and with Mercury [14]. Crystallographic data are
collected in Table 3. CCDC-930616 (Fe2-Cl) and -930617 (Fe3-I)
Z. Anorg. Allg. Chem. 2013, 1498–1503 © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
contain the supplementary crystallographic data for this paper. These
data can be obtained free of charge from the Cambridge Crystallo-
graphic Data Center via www.ccdc.cam.ac.uk/data_request/cif.
Supporting Information (see footnote on the first page of this article):
contain the tabulated temperature dependent NMR spectroscopic data
of the five complexes discussed in this manuscript (Tables S1–S5), the
temperature dependent magnetic measurements of the complexes
Fe1-Cl, Fe2-Cl and Fe3-Cl (Figure S1) and the observed shift of the
1
H NMR signals of Fe2-Cl plotted against 1/T (Figure S2).
Acknowledgments
We gratefully acknowledge financial support from the Fonds der
Chemischen Industrie. We thank P. Mayer and S. Albrecht (AK
Klüferes, University of München) for collecting the data of the X-ray
structures. This Article is in memory of the late Professor Ernst-
Gottfried Jäger, who inspired the work on these complexes.
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Received: March 26, 2013
Published Online: May 24, 2013
www.zaac.wiley-vch.de 1503