Dipyrromethene-Triazolylidene Silver Complexes: Synthesis, Structure and Opportunities

Article abstract of DOI:10.1002/ejic.202000805

The synthesis and characterization of unusual silver triazolylidene-containing dipyrromethene complexes are described. The carbene TAD-N₃C-H obtained from its parent Triazole-Appended Dipyrromethene (TAD-N₄) is an excellent ligand fo

Full text of DOI:10.1002/ejic.202000805

European Journal of Inorganic Chemistry
Accepted Article
Title: Dipyrromethene-Triazolylidene Silver Complexes: Synthesis,
Structure and Opportunities
Authors: Aurélie RAGO, Charles GUERIN, Eric FRAMERY, Ludivine
JEAN-GERARD, Clothilde COMBY-ZERBINO, Philippe
DUGOURD, and Bruno ANDRIOLETTI
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.202000805
Link to VoR: https://doi.org/10.1002/ejic.202000805
01/2020

10.1002/ejic.202000805
European Journal of Inorganic Chemistry
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Dipyrromethene-Triazolylidene Silver Complexes: Synthesis,
Structure and Opportunities
Aurélie Rago,[a] Charles Guérin,[a] Eric Framery,[a] Ludivine Jean-Gérard,[a] Clothilde Comby-Zerbino,[b]
Philippe Dugourd[b] and Bruno Andrioletti*[a]
[a]
[b]
A. Rago, Dr. C. Guérin, Dr. E. Framery, Dr. L. Jean-Gérard, Prof. B. Andrioletti
Institut de Chimie et Biochimie Moléculaire et Supramoléculaire, UMR CNRS 7246
Université Claude Bernard Lyon 1, Université de Lyon
43, Bd du 11 Novembre 1918, 69622 Villeurbanne Cedex, France
E-mail: bruno.andrioletti@univ-lyon1.fr; http://www.icbms.fr/casyen/research/andrioletti
C. Comby-Zerbino, Dr. P. Dugourd
Institut Lumière Matière, UMR CNRS 5306
Université Claude Bernard Lyon 1, Université de Lyon
69622 Villeurbanne Cedex, France
Supporting information for this article is given via a link at the end of the document.
Abstract: The synthesis and characterization of unusual silver
triazolylidene-containing dipyrromethene complexes are described.
The carbene TAD-N3C-H obtained from its parent Triazole-Appended
Dipyrromethene (TAD-N4) is an excellent ligand for the complexation
of silver, thanks to the proximity between the dipyrromethene scaffold
and the triazolylidene. The effect of silver salt stoichiometry on the
structure of the complexes was clearly evidenced by 1H-NMR
spectroscopy and mass spectrometry. Furthermore, an unexpected
argentophilic interaction was proved by different analytical techniques,
including X-Ray diffraction analysis and fluorescence spectroscopy.
The potentiality of using the unprecedented DPM-triazolydene silver
complexes for the preparation of dipyrromethene-based
metallocomplexes displaying unusual coordination mode was further
demonstrated with palladium.
complex is isolated. Generally, the silver atom interacts with
pyrrole double bonds through  interactions.[23]
For several years, our group has been involved in the synthesis
and the study of a family of functionalized dipyrromethenes, the
Triazole-Appended Dipyrromethenes (TADs) (Figure 1). In
particular, we have shown that the TAD-N4-derived BODIPYs
present excellent optical properties, both in organic and in
aqueous solution.[24] In addition, Zn-TAD-N4-metallocomplexes
have recently been proven efficient as catalyst for the carbonation
of epoxides.[25] In parallel, the corresponding triazolium salt TAD-
N3C-H has shown good promises in anion recognition, particularly
- [26]
with BF4 .
Dipyrromethenes (DPM) have been studied in the literature.[1]
They constitute key building blocks in the synthesis of pyrrolic
macrocycles.[2] Also, their BF2-complexes (BODIPYs) are well-
known for their remarkable optical properties.[3] DPMs present a
strong affinity for a large variety of metals, and can be
functionalized to afford metallocomplexes displaying original
structures with applications in catalysis,[4–8] luminescence[9,10] or
in the construction of supramolecular assemblies.[11–13]
Most commonly, phosphine[14–16] and carbene[17–21] ligands are
used to synthetize silver complexes. In particular, they play a key
role in transmetalation reactions. Unexpectedly, to the best of our
knowledge, there is only one example of DPM-Ag complex,
obtained by addition of a base and (Ph3P)AgOTf on an
azadipyrromethene solution.[22] In these conditions, a trigonal
Figure 1. TAD-N4 and TAD-N3C-H general structures
Among the large potential of this ligand, its easy conversion to the
corresponding mesoionic carbene (MIC) after triazole salt
deprotonation with a relatively weak base has caught our attention.
Triazolylidenes have been described for the first time in 2008 by
Albrecht and coll.[27] and have been widely investigated since.
Interestingly, they are obtained efficiently from the corresponding
triazole, and can be easily functionalized. Many examples of
triazolylidene-metal complexes have been described in the
literature.[28] They can be obtained by direct metalation, by free-
1
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10.1002/ejic.202000805
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COMMUNICATION
carbene generation followed by metal complexation or by
transmetalation of a silver complex. The most common metals
used for the transmetalation are palladium,[29–32] iridium,[33–35]
rhodium,[36–39] ruthenium,[40–43] or gold.[44–46] The corresponding
complexes are commonly used as catalysts in various
transformations such as cross-coupling,[47–49] α-arylation,[49]
hydrogenation,[35,40–42,50] or in the synthesis of oxazolines.[44,51]
Generally, the intermediate silver complexes are not isolated, the
second source of metal being added in the reaction medium in
situ. A few examples of silver-triazolylidene complexes have been
described in the literature. For example, Heath et al. have
reported on the formation of a linear triazolylidene-Ag-X complex
with the addition of silver oxide onto the ligand.[51] The dimer-
complex can also be observed, with the coordination of the metal
between two triazolylidene ligands.[52] When the ligand
incorporates other chelating sites, it is possible to obtain
complexes displaying original structures with less common
geometries, including Ag-Ag interactions.[53]
Next, complexation with silver oxide was explored. This source of
silver is commonly used in carbene chemistry. Indeed this salt
offers the possibility to deprotonate and metalate at the same time
without adding another base.
The TAD-N3C-H ligand displays several acidic protons in different
environments (Figure 2). The triazolium proton is the more
acidic.[54,55] However, the metalation of the DPM and the triazole
can be considered, leading to the formation of different structures
(Figure 2). Interestingly, the deprotonation-complexation
sequence could easily be monitored by 1H NMR as the acidic
protons appear at different chemical shifts (Figure 3, a). Indeed,
the triazole proton signal appears at δ = 8.70 ppm (in blue) and
the triazolium salt proton signal appears at δ = 10.25 ppm (in
orange).
Herein, we describe the synthesis and the metalation of the
TAD-N3C-H ligand with silver. The presence of the triazolylidene
in α-dipyrromethene position was proven to play a key role in the
binding mode. The fine control of the amount of silver appeared
essential for controlling the structure of the expected silver
complexes.
The TAD-N4 ligand was synthesized in three steps from 2-
dibromoethene-N-tosylpyrrole 1 according to the methodology
developed in our group (Scheme 1).[24] After a Corey-Fuchs
reaction followed by a Huisgen cycloaddition, compound 2 was
isolated in 66% yield. Next, the nitrogen atom deprotection
afforded the “half” ligand 3 in 88% yield. After condensation and
oxidation, the targeted TAD-N4 ligand was isolated in 74% yield.
After mono-methylation of the TAD-N4 ligand with methyl iodide in
toluene at 65 °C during 24 hours, the triazolium salt TAD-N3C-H
was obtained in 92% yield. Noticeably, no trace of the bis-
methylated adduct was observed at this temperature.
Figure 2. TAD-N3C-H-acidic protons and possible coordination modes
Scheme 1. Synthesis of TAD-N4 and TAD-N3C-H ligands. Reagents and
conditions: (i) n-BuLi, THF, -78 °C, 4 h; (ii) azidocyclopentane, CuSO4.5H2O,
sodium ascorbate, benzoic acid, t-BuOH/H2O, rt, 12 h; (iii) 5M aq. NaOH, TBAB,
dioxane/H2O, reflux, 24 h; (iv) methyl 4-formylbenzoate, TFA, DCM, rt, 12h then
p-chloranil, 35 °C, 1 h; (v) MeI, toluene, 65 °C, 24 h.
Figure 3. In situ 1H NMR spectra (300 MHz, CD2Cl2) of the silver complex
obtained after 24 h at 40 °C with different silver amounts.
2
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10.1002/ejic.202000805
European Journal of Inorganic Chemistry
COMMUNICATION
were proven very stable in solution even after ageing. Indeed, after 6
months, the mass spectrum of the sample revealed the presence of
(TAD-N3C)2Ag(AgI2) as the only remaining product in solution.
Inspired by the work of Hayes et al.[56], the following mechanism
(Scheme 2) is proposed for explaining the formation of the two
complexes. Firstly, Ag2O deprotonates the triazolium and
coordinates to the newly formed carbene affording the first neutral
complex TAD-N3C-Ag(I) and silver hydroxide (Scheme 2, a). The
release of AgOH allows a second deprotonation/complexation
sequence on an additional molecule of TAD-N3C-H with water
release (Scheme 2, b).
The complexation was carried out at 40 °C in deuterated
dichloromethane. After the addition of one equivalent of silver
oxide to a solution of TAD-N3C-H (Figure 3, b), the 1H NMR
spectrum displayed two well-defined signals in the triazole proton
area at δ = 9.04 and 9.19 ppm. At 8.84, 8.88 ppm and 9.44 ppm,
three broader signals were observed but it was not possible to
assign them unambiguously to any structure. However, on the
basis of precedents from the literature[28] and mass spectrometry
analyses (see Supplementary Information), it is likely that those
signals reveal an equilibrium between the neutral TAD-N3C-Ag(I)
and the cationic (TAD-N3C)2Ag(AgI2) forms of the silver-TAD
complexes (Scheme 2). Noticeably, the silver-carbene complexes
Scheme 2. Mechanistic proposition for the complexation with one equivalent of silver oxide
The reaction was repeated with 1.5 equivalent of silver oxide.
Wagner et al. in the case of a imidazolylidene-silver-pyridine
1
Under these conditions, the H NMR revealed the formation of
dimer complex,[57] where the Ag-Ag distance reached 2.89 Å. It is
also similar with the complex described by Cai et al. where the
distance Ag-Ag was 2.84 Å.[53] The C26-Ag1 and C58-Ag2 bonds
are similar (~ 2.10 Å), which is common for a carbene-silver bond.
another compound (Figure 3, c) in 70% NMR yield. The latter
could be crystallized by slow diffusion of pentane in the CD2Cl2
NMR solution. The X-ray diffraction analysis (CCDC number:
1997118) revealed a dimer structure with the chelation of a silver
atom by the dipyrromethene, the triazolylidene and a Ag-Ag bond
(Figure 4). On the dipyrromethene scaffold, planar distortions of
the pyrroles of 25.5° and 21.0° respectively were observed for the
two ligands. The N1-Ag2 and N10-Ag1 distances were similar
(2.16 and 2.18 Å, respectively) whereas the N2-Ag2 and N9-Ag1
bonds were longer (2.56 and 2.47 Å, respectively). An
argentophilic interaction was observed, with a Ag1-Ag2 distance
of 2.97 Å. Hence, each silver atom sits in a deformed triangular-
based pyramidal environment. Such an environment and the
interatomic distances are comparable with those described by
3
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10.1002/ejic.202000805
European Journal of Inorganic Chemistry
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observe large bands related to the Ag-Ag interactions leading to
the formation of a Ag-Ag* excimer under irradiation. Consequently,
the stabilization induced by the Ag-Ag bond results in a smaller
HOMO-LUMO gap allowing a radiative relaxation of the complex.
Fluorescence measurements (Figure 5) of the silver complex
solution confirmed the existence of the (TAD-N3C)2Ag2 dimer.
Unfortunately, in agreement with precedents from the literature,[57]
the life time of the excimer was too short to be measured.
Noticeably, the Stokes shift was about 42 nm which is lower than
what it is generally observed.
Figure 5. Normalized absorption (plain line) and emission (dotted line) of (TAD-
N3C)2Ag2 in DCM
Figure 4. Different views of (TAD-N3C)2Ag2 molecular structure - all hydrogen
atoms were omitted for clarity
On the basis of the solid state and solution analyses, the following
mechanism explaining the formation of the (TAD-N3C)2Ag2
complex is proposed (Scheme 3). First, in the presence of Ag2O,
the DPM core undergoes a silver-assisted (intermediate A)
deprotonation allowing the formation of the silver complex B and
AgI which precipitates in the reaction medium. Similarly to Ag2O,
AgOH can deprotonate the complex B affording (TAD-N3C)2Ag2,
H2O and AgI.
To confirm the existence of (TAD-N3C)2Ag2, several analyses
were carried out. The molecular ion observed in the MS spectrum
confirmed the existence of the (TAD-N3C)2Ag2 complex (m/z =
1337 uma for [M+H]+). Argentophilic interactions, as well as
aurophilic interactions, display specific features. In particular,
LMCT (Ligand to Metal Charge Transfer) transitions are observed
in a silver complex without any Ag-Ag interaction. Conversely,
LMMCT transitions (Ligand to Metal-Metal Charge Transfer)
reveal Ag-Ag interactions.[58–60] Particularly, it is possible to
4
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10.1002/ejic.202000805
European Journal of Inorganic Chemistry
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Scheme 3. Mechanistic proposition for the formation of (TAD-N3C)2Ag2
In the presence of larger amounts of Ag2O (i.e. 2 or 5 equivalents;
Figure 3, d-e), the signal at 9.05 ppm assigned to the triazole C-
H tends to disappear. Hence, the excess Ag2O is able to
deprotonate the triazole C-H affording the corresponding
triazolide that can further bind to silver. While a coordination of
the triazolide to the DPM bound-silver atom was expected, the
formation of oligomers (or short polymers) was evidenced by MS
analyses. Unfortunately, the structure of resulting coordination-
polymer could not be totally elucidated, even if the UV-Vis
analyses confirmed that the Ag-DPM bonds remained (λmax = 551
nm with 5 equivalents of Ag vs λmax = 547 nm with 1.5 equivalent
of Ag and λmax = 534 nm for the ligand).
Scheme 4. Transmetalation with palladium
This work clearly demonstrates that it is possible to form silver
complexes from TAD-N3C-H and possibly transmetalate the
corresponding silver complexes to afford new DPM complexes. In
the presence of one equivalent of silver oxide, an equilibrium
between two triazolylidene-silver complexes was obtained without
any contribution of the DPM scaffold. Interestingly, with 1.5
equivalent of silver oxide, a dimer was isolated. The X-Ray
diffraction analysis of the dimer revealed the involvement of the
DPM scaffold in the coordination of silver and the existence of an
argentophilic interaction, which was further confirmed by
fluorescence analysis, with the observation of a characteristic
band for the Ag-Ag bond. In the presence of larger amounts of
Ag2O, a coordination polymer was obtained but it could not be
Next, the possibility to transmetalate the silver DPM-carbene with
palladium was attempted. In the presence of an excess of
PdCl2(MeCN)2, the in-situ generated (TAD-N3C)2Ag2 complex
was converted to the corresponding TAD-N3C-Pd(Cl) complex in
55% yield after purification on alumina (Scheme 4). Hence, the
possibility to transmetalate the silver complexes was proven.
Work is currently ongoing in our laboratory to investigate further
this strategy and allow the preparation of unprecedented DPM-
metallocomplexes.
5
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This work was supported by the Ministère de l’Enseignement
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Keywords: Carbene ligands • Metal-metal interactions • N
ligands • Neighboring-group effects • Silver
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10.1002/ejic.202000805
European Journal of Inorganic Chemistry
COMMUNICATION
Entry for the Table of Contents
Key topic: Silver carbene complexes
An unexpected silver-triazolylidene-dipyrromethene complex is described. Through this example, we evidence the crucial role of the
stoichiometry in silver to afford unprecedented dipyrromethene silver complexes.
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This article is protected by copyright. All rights reserved.