Investigation of Cyclam Based Re-Complexes As Potential Electrocatalysts For The CO Reduction Reaction

Journal of Inorganic and General Chemistry
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DOI: 10.1002/zaac.202000450 ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Investigation of Cyclam Based Re-Complexes as Potential

Electrocatalysts for the CO2 Reduction Reaction
Philipp Gerschel,[a] Anna L. Cordes,[a] Sarah Bimmermann,[a] Daniel Siegmund,[b]
Nils Metzler-Nolte,[a] and Ulf-Peter Apfel*[a, b]
Dedicated to Professor Dr. Peter Klüfers on the Occasion of his 70th Birthday
Among the various homogenous electrocatalysts, especially attention. Herein, we report on a series of cyclam based Re
Re(bpy)(CO)3Cl and [Ni(cyclam)]2 + were shown to be highly complexes comprising the original {N4} as well as heteroatom-
efficient for the selective conversion of CO2 to CO at moderate altered ligand frameworks, describe their synthesis, reveal their
potentials. However, a purposeful combination of a ReI coordination behavior and furthermore investigate their per-
tricarbonyl unit with a cyclam ligand hitherto received no formance towards the electrochemical CO2 reduction.
Introduction demands, suitable strategies are required to achieve a selective

and low-energy conversion.[1,2,10,11]
The earths major greenhouse gas, CO2, contributes massively to Among the variety of CO2 reduction approaches, electro-
the current global warming with a global radiative forcing of at catalysis was suggested to be the most promising and
least 2.076 W m 2, which accounts to 66 % of the total sustainable, as it can be run directly with renewable
anthropogenic radiative forcing.[1–5] Since the ever-increasing power.[2,12–14] However, finding suitable electrocatalysts that
global warming triggers an unstoppable climate change, which operate at low overpotentials and with a high selectivity for the
in turn affects the environment and its ecological systems CO2 reduction is challenging.[15–17] Although heterogeneous
adversely, a decrease of further CO2 emissions and a reversal of electrocatalysts are preferred for industrial applications due to
the unnaturally high concentrations of CO2 already accumulated their easy handling, high robustness and low price, homoge-
in the atmosphere is of crucial importance.[1,5–7] While the neous electrocatalysts are the key towards understanding and
avoidance of CO2 emissions can be achieved by increasing the identification of essential features for an efficient electro-
efficiency of existing energy conversion processes based on catalytic CO2 reduction reaction (CO2RR).[14,18,19] The enormous
fossil fuels and by establishing sustainable energy resources, bandwidth of homogeneous CO2RR electrocatalysts can be
the reduction of the existing high CO2 concentrations in the divided into noble metal and non-noble metal containing
atmosphere can be achieved through carbon capture and catalysts.
utilization (CCU), which deals with the chemical conversion and One of the most prominent noble metal containing electro-
utilization of CO2.[1,6,8,9] Since the activation and conversion of catalyst is Re(bpy)(CO)3Cl (1, bpy = 2,2’-bipyridine), that was first
CO2 into energy-rich products is associated with high energy described by Lehn et al. in 1984 (Scheme 1).[20] At a moderate
potential of 1.25 V vs. NHE in DMF/water (9 : 1) in the presence
of a glassy carbon working electrode, complex 1 catalyzes the
[a] P. Gerschel, Dr. A. L. Cordes, S. Bimmermann, Prof. Dr. N. Metzler-
Nolte, Prof. Dr. U.-P. Apfel selective reduction of CO2 to CO with a Faraday Efficiency (FE)
Inorganic Chemistry I of up to 98 %.[20,21] The catalytically active species was identified
Ruhr-Universität Bochum as [Re(bpy)(CO)3] , which is generated by two successive
Universitätsstraße 150 electron uptakes, with the initial being located at the bpy
44801 Bochum, Germany ligand, leaving a vacant coordination site at the Re0 center
E-mail: [email protected]
upon loss of the chloride ligand.[22–24] During catalysis, CO2 is
[b] Dr. D. Siegmund, Prof. Dr. U.-P. Apfel
Department of Electrosynthesis initially activated and bound to the vacant site of the rhenium
Fraunhofer UMSICHT center as η1-CO2H. A subsequent electron and proton uptake,
Osterfelder Straße 3
46047 Oberhausen, Germany
Supporting information for this article is available on the WWW
under https://doi.org/10.1002/zaac.202000450
© 2021 The Authors. Zeitschrift für anorganische und allgemeine
Chemie published by Wiley-VCH GmbH. This is an open access
article under the terms of the Creative Commons Attribution Non-
Commercial NoDerivs License, which permits use and distribution
in any medium, provided the original work is properly cited, the use Scheme 1. Schematic overview of complexes Re(bpy)(CO)3Cl 1, [Ni
is non-commercial and no modifications or adaptations are made. {N4}]2 + 2 and [Re(tacn)(CO)3] + 3.
Z. Anorg. Allg. Chem. 2021, 647, 968 – 977 968 © 2021 The Authors. Zeitschrift für anorganische und allgemeine Chemie
published by Wiley-VCH GmbH.
ARTICLE
accompanied by water release, generates the intermediary Results and Discussion

tetracarbonyl ReI complex [Re(bpy)(CO)4]0. In a last step, CO is
released after additional electron uptake and the catalytically Complex Syntheses and Characterization
active species is recovered.[23,24]
In order to further understand the electrocatalytic CO2RR While the {N4} ligand can be purchased, the cyclam based
performance of complex 1 a broad variety of modulations of ligand {N2S2} as well as the isocyclam based ligands {i-SN3}, {i-
the bpy ligand and furthermore substitutions of bpy for ON3} and {i-N4} itself were synthesized according to literature-
comparable ligand platforms (e. g. pyNHC, pypz, pyiz) were known procedures.[44,48] For the synthesis of the corresponding
investigated.[23–37] Among the large number of modified rhenium complexes, the macrocyclic ligands {N4}, {N2S2}, {i-N4},
rhenium complexes and within the most studied class, the 4,4’- {i-SN3} and {i-ON3} were reacted with equimolar amounts of
substituted bpy rhenium complexes, the tBu-derivative Re- Re(CO)5Br in acetone under reflux conditions. After purification
(bpy-tBu)(CO)3Cl (bpy-tBu = 4,4’-di-tert-butyl-2,2’-bipyridine) is via recrystallization, the desired rhenium complexes Re{N4} (=
particularly noteworthy. [Re(k3-N,N,N-{N4}(CO)3]Br, 87 %), Re{N2S2} (= [Re(k3-S,S,N-
Although operating at a ~ 0.1 V higher overpotential, Re- {N2S2}(CO)3]Br, 90 %), Re{i-N4} (= [Re(k3-N,N,N-{i-N4}(CO)3]Br,
(bpy- tBu)(CO)3Cl reveals a ten times higher catalytic activity 74 %), Re{i-SN3} (= [Re(k3-S,N,N-{i-SN3}(CO)3]Br, 92 %) and Re{i-
compared to complex 1.[23,25] Likewise, a series of rhenium ON3} (= [Re(k3-N,N,N-{i-ON3}(CO)3]Br, 98 %) were obtained as
tricarbonyl complexes containing aniline-substituted bpy deriv- colorless solids in good yields (Scheme 2). The successful
atives with the amine function at ortho-, meta- and para- complexation and furthermore the exact composition of the
position was investigated. While the meta-version reveals the rhenium complexes was supported by electrospray-ionization
best activity within the series with a more than three times mass spectrometry (ESI-MS), revealing characteristic peaks at m/
higher turnover frequency (TOF) compared to complex 1, the z = 470.9 (Re{N4}), 504.8 (Re{N2S2}), 470.9 (Re{i-N4}), 487.9 (Re{i-
para- version shows an inhibition, likely due to coordination of SN3}) and 471.9 (Re{i-ON3}) for the corresponding [Re(L)(CO)3] +
the aniline-amine function to the reduced rhenium center.[31] fragments. Since the observed complex ions do not contain a
Among the non-noble metal containing electrocatalysts, bromine, it can be concluded that the rhenium complexes are
[Ni(cyclam)]2 + (2, cyclam = {N4} = 1,4,8,11-tetraazacyclotetra-dec- cationic and bromide acts as non-coordinating counter ion.
ane) is one of the most efficient systems with a high FE of 96 % Single crystals of complexes Re{N4}, Re{i-N4}, Re{i-SN3} and
and a reaction rate of 32 h 1 for the selective reduction of CO2 Re{i-ON3} were obtained either from acetone or methanol
to CO at a potential of 1.05 V vs. NHE at pH 4.1 in water on a solutions and provided further information about the coordina-
mercury working electrode (Scheme 1).[38–42] tion environment of the rhenium centers and binding modes of
Along this line, we recently investigated the effects the corresponding macrocycles.
regarding electrocatalytic CO2RR upon heteroatom replacement All rhenium centers are coordinated octahedrally as fac-
and geometric changes caused by the cyclam ligand.[43,44] isomers by three carbonyl ligands and additional three donor
Although N/S replacement in case of [Ni{N2S2}]2 + ({N2S2} = 1,8- atoms of the macrocycles in a k3-manner, leaving one donor
dithia-4,12-diaazacyclotetradecane) resulted in a 0.2 V de- atom of the macrocycles uncoordinated (Figure 1). Due to the
creased overpotential for the electrocatalytic CO2 reduction, the symmetry of ligand {N4} there is only one k3-isomer possible in
CO2RR selectivity was severely mindered.[43] Similar results were the case of complex Re{N4}. The averaged Re N distance of Re
obtained for the Ni-isocyclam derivative (isocyclam = {i-N4} = {N4} is 2.235 Å and the averaged Re C and C O bond lengths
1,4,7,11-tetraazacyclotetradecane), [Ni{i-SN3}]2 + ({i-SN3} = 1-thia- are 1.913 Å and 1.153 Å, respectively. Analysis of the bond
4,8,12-triazacyclotetradecane) and [Ni{i-ON3}] 2 + ({i-ON3} = 1- angles furthermore reveals that the octahedral coordination
oxa-4,8,12-triazacyclotetradecane).[44] sphere of complex Re{N4} is highly distorted with the L Re L
We herein set out to combine both mentioned approaches binding angles ranging from 102.9° to 77.8° (Table S1).
and investigated rhenium complexes bearing macrocyclic
cyclam and isocyclam based ligands for the CO2RR. Notably,
besides the synthesis and characterization of [Re(tacn)(CO)3] +
(3, tacn = 1,4,7-triaazacyclo-nonane) and its N/S or N/O heter-
oatom replaced derivatives, there are no studies on rhenium
tricarbonyl complexes comprising azamacrocyclic ligands
(Scheme 1).[45–47] We thus herein present the synthesis and
characterization of a novel series of cyclam based rhenium
tricarbonyl complexes and their electrochemical properties.
Scheme 2. Syntheses of the rhenium complexes Re{N4}, Re{N2S2}, Re

{i-N4}, Re{i-SN3} and Re{i-ON3}.
Z. Anorg. Allg. Chem. 2021, 968 – 977 www.zaac.wiley-vch.de 969 © 2021 The Authors. Zeitschrift für anorganische und allgemeine Chemie
ARTICLE
octahedral geometry in Re{i-SN3} is less distorted compared to

Re{i-N4} with L Re L binding angles ranging from 98.6° to 78.7°
(Table S1).
Unlike Re{i-SN3}, where the non-nitrogen donor atom of the
macrocycle binds to the rhenium center, in Re{i-ON3} the
oxygen atom of the {i-ON3} macrocycle remains uncoordinated.
The formation of this specific k3-isomer of Re{i-ON3} can be
justified by the HSAB concept. Since ReI is a soft transition
metal, the coordination of the comparatively softer nitrogen
donor atoms is favored over the relatively hard oxygen donor
atom. Although the k3-N coordination mode herein is geometri-
cally unfavored, Re{i-ON3} is adopting this binding mode to
avoid the coordination of oxygen. With an averaged distance of
2.253 Å the Re N bond length in Re{i-ON3} is significantly
longer compared to Re{i-N4} and slightly longer compared to
Re{N4}. The averaged Re C and C O bond lengths of Re{i-ON3}
are with 1.917 Å and 1.154 Å in a similar range as those of Re{i-
N4} and Re{N4}. However, complex Re{i-ON3} is compared to Re
{i-N4} overall less distorted with L Re L binding angles ranging
Figure 1. Molecular structures of the complexes Re{N4} (A), Re{i-N4}
(B), Re{i-SN3} (C) and Re{i-ON3} (D) shown with thermal ellipsoid from 97.6° to 79.4° (Table S1).
drawn at the 50 % probability level. Hydrogen atoms and bromide Especially for carbonyl complexes, IR spectroscopy is a
counterions are omitted for clarity. Gray: carbon, blue: nitrogen, valuable tool in order to gain information about the geometry
yellow: sulfur, red: oxygen and dark blue: rhenium. and symmetry of the complexes and to determine the effects of
the remaining ligands on the electronic properties of the metal
center. The IR spectra of complexes Re{N4}, Re{N2S2}, Re{i-N4},
In contrast to {N4}, three k3-isomers are possible for the Re{i-SN3} and Re{i-ON3} reveal a similar band structure in the
simplest structurally related ligand {i-N4}. However, only one carbonyl region, with a sharp band over 2000 cm 1 and a broad
isomer is obtained in case of Re{i-N4} with the nitrogen atom band around 1900 cm 1, which is characteristic for [Re(L)(CO)3] +
between the propyl units uncoordinated. With an averaged fac-isomers (Figure 2).[46] However, within the different rhenium
Re N distance of 2.214 Å the nitrogen atoms in Re{i-N4} are complexes there are small alterations in the general band
slightly stronger bonded to the rhenium center compared to Re structure, that can be explained by the different donor atom
{N4}. However, the averaged Re C and C O bond lengths of Re sets and the differently distorted octahedron geometries. While
{i-N4} remain comparatively equal with 1.912 Å and 1.150 Å. for all k3-N complexes Re{N4}, Re{i-N4} and Re{i-ON3} the sharp
Furthermore, bond angle analysis shows that the octahe-
dron of Re{i-N4} is overall less distorted compared to Re{N4}
(Table S1).
Similar to ligand {i-N4}, three k3-isomers for the correspond-
ing [Re(k3-{L})(CO)3] + complexes are possible for the ligands {i-
SN3} and {i-ON3}. While the formation of the k3-isomer of Re{i-
N4} seems to be exclusively dependent on geometrical factors,
the k3-isomer choices of Re{i-SN3} and Re{i-ON3} are additionally
dependent on the nature of the donor atoms due to the mixed
donor sets provided.
In case of Re{i-SN3} the sulfur donor atom of the macrocycle
binds to the rhenium center and similar to Re{i-N4} the nitrogen
atom between the propyl units remains uncoordinated. The
formation of this specific k3-isomer is favored by two factors.
On the one hand the complex occupies a preferred thermody-
namic geometry and on the other hand sulfur is coordinated as
preferred donor atom according to the HSAB concept. Complex
Re{i-SN3} has a Re S distance of 2.456 Å and an averaged Re N
bond length of 2.237 Å. Moreover, due to the influence of the
sulfur donor atom the Re C bond lengths is altered significantly
compared to Re{i-N4}. While the averaged C O distance of Re{i- Figure 2. Solid ATR-IR spectra of the rhenium complexes Re{N4}
SN3} is maintained with 1.150 Å, the averaged Re C bond (red), Re{N2S2} (blue), Re{i-N4} (yellow), Re{i-SN3} (green) and Re{i-
length is comparatively elongated with 1.928 Å, indicating a ON3} (violet). For comparison, the band positions of Re{N4} are
weaker π-backbonding in case of Re{i-SN3}. Moreover, the shown as grey dotted lines.
ARTICLE
CO band is observed at ~ 2014 cm 1, for the k3-S/N complexes complex Re{N2S2} twenty signals are observed in the corre-
Re{i-SN3} (2019 cm 1) and Re{N2S2} (2027 cm 1) the same CO sponding 13C{1H} NMR spectrum, indicating either an equili-
band is observed at higher wavenumbers with increasing sulfur brium between the two possible k3-isomers or the presence of
content. This finding indicates a weaker π-backbonding of the two different conformational isomers in solution (Figure S2). In
carbonyl ligands upon sulfur coordination, which is in line with case of the, according to their crystal structures, C2v symmetric
the Re C and C O bond length analysis of complex Re{i-SN3}. isocyclam based complexes Re{i-N4}, Re{i-SN3} and Re{i-ON3},
While the CO band at higher wavenumbers seems to depend five different signals are expected in their 13C{1H} NMR spectra
mainly on the donor atoms nature of the macrocycles, the for the corresponding macrocyclic ligand. However, all 13C NMR
broad CO band at lower wavenumbers depends additionally on spectra of the complexes Re{i-N4}, Re{i-SN3} and Re{i-ON3}
the geometry of the complexes. Here again the sulfur reveal additional signals besides the expected dominant five
coordination causes a shift of the broad band to higher signals, also indicating the presence of different k3-or conforma-
wavenumbers for Re{N2S2} and Re{i-SN3}, while a less distorted tional isomers in solution (Figures S3–S5).
octahedron geometry, like in cases of Re{i-N4}, Re{i-SN3} and Further investigations of the rhenium complexes using UV/
especially Re{i-ON3}, causes a shift to lower wavenumbers vis/NIR spectroscopy show in all cases a similar double
(Figure 1 and Table 1). absorption band structure in the UV region around 320 nm,
Although no molecular structure of complex Re{N2S2} was whereby the exact band positions of the rhenium complexes
obtained, we can now predict the k3-binding mode of the differ only by 1–2 nm (Table 1 and Figure S6). Furthermore,
{N2S2} ligand based on the IR data of complexes Re{N2S2} and while in case of the k3-N complexes Re{N4}, Re{i-N4} and Re{i-
Re{i-SN3} and the molecular structure of Re{i-SN3}. Since the CO ON3} the band at lower wavelengths can be seen as shoulder of
bands of Re{N2S2} are observed at significantly higher wave- the absorption at higher wavelengths, the same band is more
numbers compared to the bands of complex Re{i-SN3}, where pronounced in case of the k3-S/N complexes Re{N2S2} and Re{i-
one sulfur atom is coordinated to the rhenium center, and the SN3} and can be seen as discrete band.
coordination of sulfur atoms is known to result in a weaker π-
backbonding, complex Re{N2S2} is most likely the k3-S,S,N
isomer. Electrochemical Characterization
While the thermodynamically preferred coordination modes
of the rhenium complexes Re{N4}, Re{i-N4}, Re{i-SN3} and Re{i- All rhenium complexes Re{N4}, Re{N2S2}, Re{i-N4}, Re{i-SN3} and
ON3} in the solid state were revealed by crystal structure Re{i-ON3} were characterized by cyclic voltammetry (CV) in dry
analyses, no information is provided about the structures in acetonitrile with 0.1 M [nBu4N]PF6 as supporting electrolyte in
solution. In order to shed light on the structures of the rhenium an argon atmosphere at a scan rate of 100 mV s 1 (Figure 3).
complexes in solution 13C{1H} NMR spectroscopic experiments in Comparison of the CVs of the different complexes reveals
deuterated methanol were carried out. Since for the C1 that all rhenium complexes have the same shape and features
symmetric complex Re{N4} only one k3-isomer is thinkable, ten in their voltammograms. At potentials more negative than
different signals for the macrocyclic ligand are expected and 2.30 V vs. Fc/Fc + they show an irreversible ReI/0 redox couple
found in the corresponding 13C{1H} NMR spectrum (Figure S1). and at potentials more positive than 0.35 V vs. Fc/Fc + they
Contrary to complex Re{N4}, in case of the C1 symmetric show an irreversible ReII/I redox couple. In all cases, the
mentioned ReI/0 and ReII/I couples stay fully irreversible, when
altering the scan rate (Figures S7–S11).
Although the CVs of all rhenium complexes have the same
Table 1. Characteristic IR and UV spectroscopic features and shape, the individual complexes differ significantly in their
electrochemical data of complexes Re{N4}, Re{N2S2}, Re{i-N4}, Re{i-
cathodic peak potentials Epc for the ReI/0 couple (Table 1).
SN3} and Re{i-ON3}.
Compared to Re{N4}, which reveals an Epc of 2.68 V vs. Fc/Fc +
complex IR solid UV MeCN Epc[a] MeCN Epc[a] MeCN/ for the ReI/0 couple, the exchange of two nitrogen donor atoms
~v (cm 1) λ (nm) (V) H2O (V)
against sulfur while maintaining the ligand geometry leads to
Re{N4} 2014 317 2.68 2.55 an anodic shift of the Epc by 0.37 V to 2.31 V vs. Fc/Fc +, as in
1898 322 (sh) the case of Re{N2S2}. Changing the geometry compared to Re
1880 {N4} while maintaining the donor atoms, as in the case of Re{i-
Re{N2S2} 2027 318 2.31 2.23 N4}, also results in an anodic but comparatively smaller shift of
1906 324
the Epc by 0.1 V to 2.57 V vs. Fc/Fc +. When combining the
Re{i-N4} 2014 318 2.57 2.47
1873 323 (sh) effects of geometric change and donor atom exchange, which
Re{i-SN3} 2019 318 2.56 2.31 individually cause a shift of the Epc to more anodic potentials, a
1886 324 more anodic Epc would be expected in the case of Re{i-SN3}
Re{i-ON3} 2015 318 2.69 2.48 compared to Re{i-N4}. However, with 2.56 V vs. Fc/Fc + the Epc
1894 323 (sh) of Re{i-SN3} remains unaltered compared to Re{i-N4}. Further-
1875
more, complex Re{i-ON3}, with the actual unfavored k3- N
1853
geometry shows an expected and compared to Re{i-N4} more
[a] Cathodic peak potential vs. Fc/Fc + at 100 mV s 1. cathodic Epc of 2.69 V vs. Fc/Fc + for the ReI/0 redox couple.
ARTICLE
The anodic peak potentials Epa for the ReI/II couple also differ
for the individual rhenium complexes. However, the difference
between all complexes is much less pronounced and within a
range of 80 mV. Moreover, the Epc for the ReI/0 couple is more
relevant compared to the Epa for the ReII/I couple, since the Re0
species is expected to be the potentially catalytic active species
for the CO2 reduction reaction.
Finally, the electrochemical properties of complexes Re{N4},
Re{N2S2}, Re{i-N4}, Re{i-SN3} and Re{i-ON3} were analyzed in an
acetonitrile/water mixture (4 : 1), since water acts as proton
source for the later examined electroreduction of CO2 (Figure 4,
dashed lines).
The CVs of the rhenium complexes in the presence of water
reveal the same features as the measurements in pure
acetonitrile. All complexes show a fully irreversible ReI/0 couple
and a compared to the measurements in pure acetonitrile
slightly more reversible ReII/I couple. While the ReI/0 couples of
all rhenium complexes and the ReII/I couples of Re{N2S2}, Re{i-
N4} and Re{i-SN3} stay irreversible when increasing the scan
rate, the nature of the ReII/I couples of Re{N4} and Re{i-ON3} can
be identified as quasi-reversible based on the measurements
with increased scan rates (Figures S12–S16).
Although in presence of water the cathodic peak potentials
of the ReI/0 couples are generally shifted to more anodic
Figure 3. Cyclic voltammograms of 1 mM solutions of complexes potentials compared to the measurements in acetonitrile, the
Re{N4}, Re{N2S2}, Re{i-N4}, Re{i-SN3} and Re{i-ON3} in acetonitrile individual shifts of the rhenium complexes are different
with 0.1 M [nBu4N]PF6 at 100 mV s 1. (Table 1). While for complexes Re{N4}, Re{N2S2} and Re{i-N4} the
potential shift is around 0.1 V, the shift for complexes Re{i-SN3}
and Re{i-ON3} is with 0.2 V significantly higher.
Figure 4. Cyclic voltammograms of 1 mM solutions of complexes Re{N4}, Re{N2S2}, Re{i-N4}, Re{i-SN3} and Re{i-ON3} in acetonitrile/water
(4 : 1) under argon (dashed lines) and saturated with CO2 (solid lines) with 0.1 M [nBu4N]PF6 at 100 mV s 1.
ARTICLE
After saturation of the acetonitrile/water (4 : 1) solutions of Table 2. Quantification of the gaseous electrolysis products by
the rhenium complexes with CO2, the shape of the CVs changed GC-MS.
drastically in all cases compared to the measurements in an
complex ECPC[a] Time FEH2 FECO Q TON[b]
argon atmosphere (Figure 4, solid lines). In the presence of CO2 (V) (h) (%) (%) (C)
a significant reductive current increase is observed for com-
plexes Re{N4}, Re{N2S2}, Re{i-N4} and Re{i-ON3} after generation blank 2.68 2 78 2.1 0.12
4 69 0.2 0.35
of the Re0 species, indicating a potential interaction with CO2.
6 89 0.5 1.5 -
For complex Re{i-SN3}, the same kind of current increase is 8 95 0.3 3.7
observed, however, much less pronounced. Moreover, a much 24 96 0.7 22.3
higher reductive current maximum ipc around 100 μA is Re{N4} 2.68 2 53 4.8 0.17
observed for all k3-N complexes Re{N4}, Re{i-N4} and Re{i-ON3}, 4 67 7.4 0.56
compared to the ipc around 40 μA observed for the k3-S,N 6 63 9.3 1.0 0.90
8 69 11 1.4
complexes Re{N2S2} and Re{i-SN3}. Furthermore, in the presence
24 57 11 3.9
of CO2 all complexes reveal an additional oxidative signal prior Re{N2S2} 2.47 2 46 4.5 0.12
the wave associated with the ReII/I redox couple. This oxidation 4 56 4.5 0.22
peak only appears when generating the Re0 species beforehand. 6 44 4.7 0.31 0.08
If the CV scan is performed solely in oxidative direction, the 8 53 4.9 0.43
wave is missing in all cases (Figure S17). This finding further 24 41 4.9 1.56
Re{i-N4} 2.59 2 44 13 0.47
suggests that the electrochemically generated Re0 species 4 56 15 1.3
interact with CO2 and potentially catalyze its reduction. 6 69 18 2.3 4.10
Analysis of the icat/ipc ratios of the complexes Re{N4} (1.63), 8 70 17 3.6
Re{N2S2} (1.45), Re{i-N4} (1.66), Re{i-SN3} (1.14) and Re{i-ON3} 24 75 6.9 22.4
(2.15) in acetonitrile/water (4 : 1) shows that the catalytic Re{i-SN3} 2.35 2 89 2.9 0.10
4 83 7.0 0.40
activities of the rhenium complexes studied here are signifi-
6 76 7.3 0.75 0.62
cantly lower compared to the benchmark electrocatalysts 8 72 7.8 1.0
Re(bpy)(CO)3Cl (4.4 in anhydrous acetonitrile, 13.4 in 24 69 6.5 4.0
acetonitrile + 4 % TFE) and [Ni(cyclam)]2 + (~ 4 in acetonitrile/ Re{i-ON3} 2.61 2 52 10 0.14
water (4 : 1)).[31,49] 4 60 7.7 0.33
6 45 7.9 0.62 0.93
8 44 11 0.90
24 49 21 3.1
Electrocatalytic CO2 Reduction
[a] Potential of the controlled potential coulometry vs. Fc/Fc +. [b]
Turnover number (TON) of all CO2 reduction based processes.
In order to determine the formed reduction products and
furthermore the amount as well as selectivity they are formed
within the catalytic regions of the different rhenium complexes,
additionally controlled potential colometry (CPC) experiments In general, during all experiments utilizing the different
were carried out (Figure S18). These long-term electrolyses were rhenium complexes only H2 and CO were obtained as gaseous
performed at defined potentials for 24 h in a one-compartment products. The complexes generally herein suppress the H2
cell using a three-electrode setup with glassy carbon as working formation which is the main reaction in the absence of any ReI
electrode, a silver wire as pseudo-reference electrode and a complex. In addition, after 24 h of electrolysis, none of the
platinum wire as counter electrode. After saturation of the experiments showed the formation of a deposited species
1 mM rhenium complex and 0.1 M [nBu4N]PF6 containing during rinse test analysis, which would be an indication for
acetonitrile/water (4 : 1) solution with CO2, the cell was sealed catalyst decomposition or at least render the catalytically active
tightly for the time of the experiment. The CPCs with the species to be a heterogeneous one.
different rhenium complexes were carried out at the corre- Within the first 8 h of CPC with Re{N4} as catalyst, the
sponding peak potentials of the catalytic currents observed in cumulated FEs for the production of H2 and CO increased from
the presence of CO2 (Figure 4 and Table 2). During electrolysis, 58 % to 80 % during electrolysis, whereby the CO/H2 ratio
the headspace composition of the cell was analyzed every 2 h shifted from 1 : 11 to 1 : 6 in favor of CO, resulting in a FE of 11 %
within the first 8 h via GC-MS (Table 2) and after 24 h for CO after 8 h.
electrolysis, the composition of the headspace of the cell and After 24 h of electrolysis, the FE for the generation of H2
additionally the composition of the liquid phase of the cell was decreased to 57 %, while the FE for the generation of CO was
analyzed via GC-MS (Figure 5). The selectivity of the product maintained at 11 %, further improving the CO/H2 ratio. Addi-
formation utilizing the different rhenium complexes is reflected tionally, liquid phase analysis revealed formic acid with a FE of
by the Faradaic Efficiencies (FE) and in combination with the 7.2 % as well as methanol with a notably FE of 12 % as further
consumed charge the maximum amounts of formed products CO2RR products. Although the use of Re{N4} as electrocatalyst
can be determined along with a statement about the activity. reveals a low selectivity for the CO2RR with a total FE of ~ 30 %
for the sum of all CO2 reduction products, the selectivity is
ARTICLE
FE of 2.3 % were identified as further reduction products.

Although Re{i-N4} with a summed FE of ~ 19 % shows a lower
selectivity for the CO2RR compared to Re{N4}, the absolute
amounts of CO2 reduction products are significantly higher for
Re{i-N4}, since the total consumed charge and thus the activity
is almost six times higher compared to Re{N4}.
The averaged CO/H2 ratio of Re{i-SN3} is with 1 : 10 similar to
that of Re{N2S2} during the first 8 h, except for the first 2 h.
However, in contrast to Re{N2S2} the absolute FEs for Re{i-SN3}
are higher with an averaged FE of 77 % for H2 and 7.4 % for CO.
After 24 h electrolysis with Re{i-SN3} as catalyst, the FEs for the
gaseous products dropped to ~ 76 % in total, while the previous
CO/H2 ratio of 1 : 10 was maintained. Again, the liquid phase
analysis revealed formic acid and methanol as further CO2RR
products with FEs of 7.1 % and 3.9 % respectively. Compared to
Figure 5. Faradaic Efficiencies (FE, stacked bars) and total consumed
charge (red lines) after 24 h long-term electrolysis of 1 mM rhenium Re{N2S2} the CO2RR selectivity of Re{i-SN3} is significantly higher
complex solutions in CO2 saturated acetonitrile/water (4 : 1) with and comparable with that of Re{i-N4}. However, the consumed
0.1 M [nBu4N]PF6 at a defined potential. The potential during charge and consequently the catalytic activity of Re{i-SN3} is
electrolysis was held at 2.68 V vs Fc/Fc + for blank, at 2.68 V vs significantly lower compared to Re{i-N4} and comparable with
Fc/Fc + for Re{N4}, at 2.47 V vs Fc/Fc + for Re{N2S2}, at 2.59 V vs that of Re{N4}.
Fc/Fc + for Re{i-N4}, at 2.35 V vs Fc/Fc + for Re{i-SN3} and at
The FEs of Re{i-ON3} for the formation of the gaseous
2.61 V vs Fc/Fc + for Re{i-ON3}. Gray: hydrogen (H2), blue: carbon
monoxide (CO), green: formic acid (FA) yellow: methanol (MeOH) products within the first 8 h of electrolysis are relatively
and red: acetaldehyde (C CHO). constant with an averaged FE of 50 % for H2 and 9 % for CO,
resulting in an averaged CO/H2 ratio of ~ 1 : 5. However, product
analysis after 24 h of electrolysis with Re{i-ON3} as catalyst
revealed a significant shift of the CO/H2 ratio in favor of CO to
drastically increased compared to the blank measurement in almost 1 : 2, resulting in FEs for H2 and CO of 49 % and 21 %
absence of any catalyst (FECO 0.7 %). However, it must be taken respectively. Furthermore, liquid phase analysis identified
into account that the charge consumed during electrolysis in methanol as further reduction product with a remarkable FE of
presence of Re{N4} is almost six times lower compared to the 24 %. While generation of formate/formic acid during electro-
measurement without catalyst, indicating a lower total catalytic catalytic CO2 reduction is rather common,[21,51,52] the formation
activity for Re{N4}. of methanol is particularly noteworthy. Although experiments
Compared to Re{N4}, the FEs of Re{N2S2} for the formation performed in CD3CN show no incorporation of deuterium into
of the gaseous products within the first 8 h are lower and methanol or formic acid, final proof for the formation of
relatively constant with an averaged FE of 50 % for H2 and 4.7 % methanol from CO2 must be obtained by utilization of 13CO2.
for CO, resulting in an averaged CO/H2 ratio of 1 : 11. Product Consequently, an electrolysis experiment was carried out using
13
quantification after 24 h electrolysis using Re{N2S2} as catalyst CO2 and Re{i-ON3} as a proxy for all. Unfortunately, due to the
revealed a decrease in the FE for the H2 production to 41 %, lack of a suitable analytical method for these small amounts of
while the FE for the CO production was maintained at 4.9 %. methanol produced, we could not unequivocally identify CO2 as
Furthermore, liquid phase analysis showed the formation of the origin of methanol.
acetaldehyde with a FE of 18 %. However, this product While the catalytic activity of Re{i-ON3} based on the
originates from the hydrogenation of acetonitrile, rather than consumed charge is comparable to that of Re{N4} and Re{i-SN3},
CO2 reduction, as already observed in previous studies on the CO2RR selectivity of Re{i-ON3} is highest within the series of
similar nickel- and cobalt-containing complexes.[44,50] Moreover, rhenium complexes investigated herein with a total FE of 45 %.
besides the drastically lower CO2RR selectivity of Re{N2S2} One explanation for the above average CO2RR selectivity of
compared to Re{N4}, the total consumed charge and the total complex Re{i-ON3} compared to all other rhenium complexes
FE of the electrolysis with Re{N2S2} are significantly lower investigated herein is the nature of the uncoordinated donor
compared to that with Re{N4}, indicating a comparatively lower atom of the macrocyclic ligand. During the catalytic cycle a free
catalytic activity for Re{N2S2}. binding site at the rhenium center of the [Re(k3-{L})(CO)3] +
In case of Re{i-N4} the FEs for the generation of both H2 and complexes is expected, as in case of Re(bpy)(CO)3Cl.[23,24] While
CO increases gradually during the first 8 h of electrolysis, Re(bpy)(CO)3Cl only binds CO2 at this position, the [Re(k3-
reaching a plateau with a FE of 70 % for H2 and 17 % for CO. {L})(CO)3] + complexes can also bind the uncoordinated donor
Although Re{i-N4} revealed a higher FE for the production of CO atom of the macrocycle at this position and thus intrinsically
after 8 h compared to Re{N4}, the FE of Re{i-N4} for CO inhibit catalysis.[31] Since nitrogen donor atoms reveal a higher
formation dropped drastically to ~ 7 % after 24 h electrolysis, binding affinity to low-valent rhenium centers compared to
while the FE for the generation of H2 increased slightly to 75 %. oxygen donor atoms, the intrinsic inhibition in case of Re{N4},
Additionally, formic acid with a FE of 10 % and methanol with a
ARTICLE
Re{N2S2}, Re{i-N4} and Re{i-SN3} is higher compared to Re{i- were recorded with a JASCO V-670 instrument at 25 °C and are
ON3}. reported in nm.
General Procedure for the Syntheses of the Complexes [Re(k3-
{L})(CO)3]Br: Ligand {N4}, {N2S2}, {i-N4}, {i-SN3} or {i-ON3} (1 equiv.)
Conclusions was dissolved in degassed acetone (48 mL mmol 1) and Re(CO)5Br
(1 equiv.) was added to the macrocycle solution. The reaction
mixtures were heated under reflux conditions for 12 h. In all cases a
In summary, we herein describe the synthesis and character-
color change to light yellow/brown was observed. Subsequently,
ization of hitherto unprecedented cyclam based rhenium the reaction mixtures were cooled to room temperature, filtered,
complexes Re{N4}, Re{N2S2}, Re{i-N4}, Re{i-SN3} and Re{i-ON3} and concentrated. After recrystallization pure complexes Re{N4}, Re
along with their performances in the electrocatalytic reduction {N2S2}, Re{i-N4}, Re{i-SN3} and Re{i-ON3} were obtained.
of CO2. [Re(k3-N,N,N-{N4})(CO)3]Br (Re{N4}): The yellow solid obtained from
Within the series of the cyclam based rhenium complexes reaction of {N4} (50 mg, 0.25 mmol) with Re(CO)5Br (101 mg,
interesting trends are observed. Since the rhenium center 0.25 mmol) was recrystallized in hot acetone, yielding Re{N4} in
selects three of the four donor atoms of the macrocyclic ligand 87 % (120 mg, 0.22 mmol) as colorless solid. 13C{1H} NMR (75 MHz,
for coordination, a ranking of the binding affinity of ReI to CD3OD): δ = 24.6 (CH2CH2CH2), 43.9, 47.6, 48.5, 51.7, 57.7, 58.3, 59.7,
60.7 (CH2NH) ppm. ESI-MS: calcd. for [C13H24N4O3Re] + : m/z = 471.1;
different donor atoms in the order of S > N > O was revealed.
found: 470.9. EA: C13H24BrN4O3Re: calcd. C, 28.37; H, 4.39; N, 10.18 %;
Moreover, it was shown that in case of the isocyclam derivatives found: C, 28.47; H, 4.59; N, 10.35 %. IR (ATR): ~v = 3395, 3059, 2907,
the k3-coordination mode, which leaves the donor atom 2872, 2826, 2014, 1898, 1880, 1468, 1055, 1024 cm 1. UV/vis/NIR
between the propyl units uncoordinated, is preferred due to (CH3CN): 317, 322 (sh) nm.
the minimized ring strains. [Re(k3-S,S/N,N-{N2S2})(CO)3]Br (Re{N2S2}): The yellow/brown solid
Regarding the electrocatalytic CO2 reduction, all rhenium obtained from reaction of {N2S2} (50 mg, 0.21 mmol) with Re(CO)5Br
complexes reveal a significant increase in CO2RR selectivity (87 mg, 0.21 mmol) was recrystallized using a mixture of acetone
compared to the measurement in absence of any catalyst. and methanol as solvent and diethyl ether as precipitant. Complex
However, H2 remains the major reduction product in all cases. Re{N2S2} was obtained as colorless solid in 90 % (110 mg,
0.19 mmol) yield. 13C{1H} NMR (75 MHz, CD3OD): δ = 24.5, 27.2, 27.5,
While Re{i-N4} shows the highest catalytic activity within the
28.5 (CH2CH2CH2), 28.8, 29.4, 29.7, 30.2, 30.7, 31.9, 32.5, 37.5 (CH2S),
series, Re{i-ON3} reveals the highest CO2RR selectivity after 24 h 39.1, 47.4, 47.7, 51.0, 53.7, 54.4, 57.4, 62.3 (CH2NH) ppm. ESI-MS:
with a total FE of 45 %, which in turn is split into 21 % CO and calcd. for [C13H22N2O3ReS2] + : m/z = 505.1; found: 504.8. EA:
24 % methanol. The remaining complexes can be ranked C13H22BrN2O3ReS2 + 0.33 CH3OH + 0.67 H2O: calcd. C, 26.37; H, 4.09;
according to their CO2RR selectivity from Re{N4} > Re{i-N4} > Re N, 4.61 %; found: C, 26.25; H, 4.00; N, 4.72 %. IR (ATR): ~v = 3400,
{i-SN3} > Re{N2S2}, where Re{N2S2} has only a FE of 4.9 % for the 2937, 2814, 2735, 2027, 1906, 1448, 1045, 1018 cm 1. UV/vis/NIR
(CH3CN): 318, 324 nm.
production of CO.
Notably, in comparison to the literature known electro- [Re(k3-N,N,N-{i-N4})(CO)3]Br (Re{i-N4}): The yellow solid obtained from
catalyst Re(bpy)(CO)3Cl, the reduction of CO2 proceeds for all reaction of {i-N4} (58 mg, 0.29 mmol) with Re(CO)5Br (117 mg,
0.29 mmol) was recrystallized using a mixture of acetone and
herein investigated rhenium complexes at comparatively higher
methanol as solvent and diethyl ether as precipitant. Complex Re{i-
overpotentials together with a lower CO2RR selectivity. N4} was obtained as colorless solid in 74 % (118 mg, 0.21 mmol)
yield. 13C{1H} NMR (75 MHz, CD3OD): δ = 28.2 (CH2CH2CH2), 50.4,
52.7, 56.5, 61.6 (CH2NH) ppm. ESI-MS: calcd. for [C13H24N4O3Re] + : m/
Experimental Section z = 471.1; found: 470.9. EA: C13H24BrN4O3Re + 0.33 CH3OH + 0.33
H2O: calcd. C, 28.24; H, 4.62; N, 9.88 %; found: C, 28.27; H, 4.53; N,
All reactions were performed under a dry Ar or N2 atmosphere 9.77 %. IR (ATR): ~v = 3069, 2926, 2858, 2014, 1873, 1460, 1074, 1053,
using standard Schlenk techniques or by working in a glovebox. 1028 cm-1. UV/vis/NIR (CH3CN): 318, 323 (sh) nm.
Starting materials and chemicals were obtained from commercial
suppliers and used without further purification. All solvents were [Re(k3-S,N,N-{i-SN3})(CO)3]Br (Re{i-SN3}): The yellow/brown solid ob-
dried and degassed according to standard methods.[53] 1,8-Dithia- tained from reaction of {i-SN3} (50 mg, 0.23 mmol) with Re(CO)5Br
4,11-diazacyclotetradecane {N2S2},[48] 1,4,7,11-tetraazacyclotetrade- (93 mg, 0.23 mmol) was recrystallized using a mixture of acetone
cane {i-N4},[44] 1-thia-4,8,12-triazacyclotetradecane {i-SN3}[44] and 1- and methanol as solvent and diethyl ether as precipitant. Complex
oxa-4,8,12-triazacyclotetradecane {i-ON3}[44] were synthesized ac- Re{i-SN3} was obtained as light brown solid in 92 % (120 mg,
cording to literature-known procedures. NMR spectra were re- 0.21 mmol) yield. 13C{1H} NMR (75 MHz, CD3OD): δ = 28.3
corded at room temperature from the dissolved crystalline samples (CH2CH2CH2), 39.7 (CH2S), 50.3, 59.6, 62.8 (CH2NH) ppm. ESI-MS:
with a Bruker AVIII-300 NMR spectrometer and are reported in parts calcd. for [C13H23N3O3ReS1] + : m/z = 488.1; found: 487.9. EA:
per million (ppm). Unfortunately, the recorded 13C{1H} NMR spectra C13H23BrN3O3ReS + 0.25 CH3OH + 0.5 H2O: calcd. C, 27.23; H, 4.31; N,
did not show the quaternary carbon signals associated with the 7.19 %; found: C, 27.20; H, 4.09; N, 6.89 %. IR (ATR): ~v = 3425, 3055,
carbonyl ligands, and furthermore, assignment of the 1H signals 2924, 2849, 2019, 1886, 1460, 1061, 1028 cm-1. UV/vis/NIR
was not possible due to the high flexibility and anisotropy of the (CH3C N): 318, 324 nm.
complexes (Figure S19–S23). Mass spectra were obtained with a [Re(k3-N,N,N-{i-ON3})(CO)3]Br (Re{i-ON3}): The yellow solid obtained
Bruker Daltonics Esquire 6000 instrument. CHN analyses were from reaction of {i-ON3} (50 mg, 0.25 mmol) with Re(CO)5Br
measured with an Elementar vario MICRO cube. IR spectra were (101 mg, 0.25 mmol) was recrystallized using a mixture of acetone
recorded with a Bruker Tensor 27 FT-IR instrument attached with a and methanol as solvent and methanol as precipitant. Complex Re
Pike Miracle ATR unit and are reported in cm 1. UV/vis/NIR spectra {i-ON3} was obtained as colorless solid in 98 % (135 mg, 0.24 mmol)
yield. 13C{1H} NMR (75 MHz, CD3OD): δ = 26.6 (CH2CH2CH2), 50.4,
ARTICLE
56.4, 62.6 (CH2NH), 71.0 (CH2O) ppm. ESI-MS: calcd. for voltammograms, controlled potential coulometries, as well as
[C13H23N3O4Re] + : m/z = 472.1; found: 471.9. EA: C13H23BrN3O4Re + crystal structure refinements.
0.45 C3H6O: calcd. C, 29.84; H, 4.49; N, 7.28 %; found: C, 29.99; H,
4.59; N, 7.57 %. IR (ATR): ~v = 3117, 3074, 2958, 2932, 2874, 2015,
1894, 1875, 1853, 1468, 1130, 1057 cm-1. UV/vis/NIR (CH3CN): 318,
323 (sh) nm. Acknowledgements
Electrochemistry: Electrochemical studies were performed using a
This work was supported by the Fonds of the Chemical Industry
PalmSens4 potentiostat in a standard three-electrode setup in a
one-compartment cell. A glassy-carbon electrode was used as (Liebig Grant to U.-P.A. and Kekulé fellowship to P.G.), the
working electrode (WE), a Ag wire in a Luggin capillary as the Deutsche Forschungsgemeinschaft (Emmy Noether Grant to U.-
pseudo-reference electrode (PRE), and a Pt wire as the counter P.A., AP242/2-1 and AP242/5-1) and the Fraunhofer Internal
electrode (CE). The working electrode was prepared by successive Programs (Attract, Grant No. 097-602175) as well as the
polishing with 1.0, 0.3 and 0.1 μm sandpaper and subsequent Fraunhofer Cluster of Excellence CINES. Furthermore, the work
sonication in acetonitrile for 10 min. Tetrabutylammonium hexa-
was funded by the Deutsche Forschungsgemeinschaft under
fluorophosphate ([nBu4N]PF6, 0.1 M) was used as the electrolyte in
all electrochemical measurements either in anhydrous acetonitrile Germany’s Excellence Strategy, EXC-2033 (Projektnr.
or an acetonitrile/water mixture (4 : 1). Prior to each experiment, the 390677874). Open access funding enabled and organized by
electrochemical cell was degassed with Ar for 10 min. The electro- Projekt DEAL.
lyte solution was purged for 10 min either with Ar or CO2 and an Ar
or CO2 atmosphere was maintained throughout the measurement.
All cyclic voltammograms were recorded at a scan rate of Keywords: Cyclam · Rhenium · Electrocatalysis · Carbon
100 mV s 1 if not stated otherwise, and after every experiment all dioxide · Carbonyl ligands
pseudo-referenced potentials were referenced against the ferro-
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Investigation of Cyclam Based Re-Complexes As Potential Electrocatalysts For The CO Reduction Reaction

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Journal of Inorganic and General Chemistry

Investigation of Cyclam Based Re-Complexes as Potential

Introduction demands, suitable strategies are required to achieve a selective

accompanied by water release, generates the intermediary Results and Discussion

Scheme 2. Syntheses of the rhenium complexes Re{N4}, Re{N2S2}, Re

octahedral geometry in Re{i-SN3} is less distorted compared to

FE of 2.3 % were identified as further reduction products.

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