Structural Diversity and Catalytic Properties in a Family of Ag(I)-Benzotriazole Based Coordination Compounds

Article abstract of DOI:10.1021/acs.cgd.8b00960

In this work we study the coordination chemistry of a series of semirigid benzotriazole based ligands (L¹-L³) along with the low coordination number but versatile Ag^I ions. This has led to nine new coordination compounds formulated [Ag(L¹)(CF₃CO₂)] (1), [Ag₂(L^1T)₂(CF₃SO₃)₂]·2Me₂CO (2), [Ag(L^2T)(ClO₄)(Me₂CO)] (3), [Ag(L^2T)(BF₄)(Et₂O)] (4), [Ag₂(L^3T)₂(ClO₄)₂]₂ (5), [Ag(L³)(NO₃)] (6), [Ag₂(L^3T)₂(CF₃CO₂)₂] (7), [Ag₂(L^3T)(CF₃SO₃)₂] (8), and [Ag₂(L^3T)₂(CF₃CF₂CO₂)₂]·2Me₂CO (9). These compounds show structural diversity including dimers (5, 7, 9) and one-dimensional (1D) (3, 4, 6) and two-dimensional (2D) (1, 2, 8) coordination polymers. The presence of the two -CH₂- units between the three rigid backbones, benzotriazole/-C₆H₄-/benzotriazole, provides a limited, but significant, flexibility in L¹-L³, influencing their variety coordination abilities. Interestingly, certain structures exhibit an isomerism effect (L^1T-L^3T) in the benzotriazole unit when in solid state; a series of studies are indicative of the 1,1-form which is generally dominant in solution even in cases where the crystal structure does not contain this tautomer. The homogeneous catalytic efficacy of all compounds against the well-known multicomponent A³ coupling reaction and the hydration of alkynes were investigated. Compound 4 was identified as the optimal catalyst for both reactions, promoting the multicomponent coupling as well as the alkyne hydration reaction under low loadings (0.5 and 3 mol %, respectively) and in high yields (up to 99 and 93% in each case).

Full text of DOI:10.1021/acs.cgd.8b00960

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Article
Structural diversity and catalytic properties in a family
of Ag(I)-benzotriazole based coordination compounds
Edward Loukopoulos, Alaa Abdul-Sada, Eddy M. E. Viseux, Ioannis N. Lykakis, and George E Kostakis
Cryst. Growth Des., Just Accepted Manuscript • Publication Date (Web): 23 Jul 2018
Downloaded from http://pubs.acs.org on July 23, 2018
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Structural diversity and catalytic properties in a family of Ag(I)ꢀ
benzotriazole based coordination compounds
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a
a
a
*b
Edward Loukopoulos, Alaa AbdulꢀSada, Eddy M. E. Viseux, Ioannis N. Lykakis and
a
George E. Kostakis*
a
Department of Chemistry, School of Life Sciences, University of Sussex, Brighton BN1
9QJ, United Kingdom.
Eꢀmail: G.Kostakis@sussex.ac.uk
b
Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki 54124, Greece.
Eꢀmail: lykakis@chem.auth.gr
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ABSTRACT
In this work we study the coordination chemistry of a series of semiꢀrigid benzotriazole based
1
3
I
ligands (L ꢀL ) along with the low coordination number but versatile Ag ions. This has led to
1
nine
new
coordination
compounds
formulated
[Ag(L )(CF CO )]
(1),
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T
T
2T
2T
[
[
Ag (L ) (CF SO ) ]·2Me CO (2), [Ag(L )(ClO )(Me CO)] (3), [Ag(L )(BF )(Et O)] (4),
2
2
3
3 2
2
4
2
4
2
3
3T
3T
Ag
2
(L )
2
(ClO
4
)
2
]
2
(5), [Ag(L )(NO
3
)] (6), [Ag
2
(L )
2
(CF
3
CO
2
)
2
2 3 3 2
] (7), [Ag (L )(CF SO ) ]
3
T
(8) and [Ag
2
(L )
2
(CF CF CO ]·2Me CO (9). These compounds show structural diversity
3
2
2
)
2
2
including dimers (5, 7, 9), one dimensional (1D) (3, 4, 6) and two dimensional (2D) (1, 2, 8)
coordination polymers. The presence of the two ꢀCH ꢀ units between the three rigid
2
backbones, benzotriazole/ꢀC H ꢀ/benzotriazole, provides a limited, but significant, flexibility
6
4
1
3
in L ꢀL , influencing their variety coordination abilities. Interestingly, certain structures
1
T
3T
exhibit an isomerism effect (L ꢀL ) in the benzotriazole unit when in solid state; a series of
studies are indicative of the 1,1ꢀ form is generally dominant in solution even in cases where
the crystal structure does not contain this tautomer. The homogeneous catalytic efficacy of all
3
compounds against the wellꢀknown multi component A coupling reaction and the hydration
of alkynes were investigated. Compound 4 was identified as the optimal catalyst for both
reactions, promoting the multicomponent coupling as well as the alkyne hydration reaction
under low loadings (0.5 and 3 mol%, respectively) and in high yields (up to 99 and 93% in
each case).
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INTRODUCTION
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The induction of the crystal engineering concept in coordination chemistry has led to
the rational design of many novel coordination polymers (CPs) and metal organic
frameworks (MOFs) with interesting properties. One of the most promising application of
these materials is catalysis. In this context, the chosen systems may be highly tunable due to
the many possible combinations of chemical (metal selection, coordination environment and
geometry, ligand selection) and synthetic (e.g. solvent, metal(s)ꢀligand(s) ratio, temperature)
parameters, allowing for greater understanding and control of the procedure. Since the first
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,3
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6–10
reports that utilized these concepts, efforts have intensified with various oneꢀ , twoꢀ
11–13
and threeꢀdimensional coordination polymers
reactions.
being used as catalysts in a variety of
In regards to the metal selection for the construction of these coordination
architectures, Ag has been receiving increasing attention due to its rich and unique chemistry.
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Compared to other metals, Ag provides a wide range of coordination environments, with
multiple possibilities in coordination number (from 2 to 6) and geometries (e.g. linear,
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trigonal, tetrahedral, trigonal bipyramidal, square pyramidal, octahedral) . This versatility
I
I
and adaptability of Ag systems, along with the potential formation of argentophilic (Ag –
I
Ag ) interactions, has contributed significantly to the formation of peculiar structural
1
5–24
topologies
with various dimensionalities, as well as uncommon supramolecular
2
5
I
architectures . These exploits have also been crucial towards the development of Ag
coordination polymers with structural interest and potential applications, which include
26–28
28–30
31–37
38–44
luminescence
, anion exchange
, antibacterial
and catalytic activity.
Focusing
on the latter, several Ag CPs and MOFs have been especially used as catalysts in organic
45,46
transformations that involve alkyne activation
due to the supreme capability of the metal
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to form organometallic intermediates through πꢀcoordination with the carbon–carbon triple
bond.
Our group has had a longꢀstanding interest in coordination compounds derived from
semiꢀrigid organic ligands, especially Nꢀdonors. As a part of this, in previous works we
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investigated the transition metal chemistry of semiꢀrigid benzotriazoleꢀbased ligands L ꢀL
47–50
(Scheme 1), focusing on the relevant Co and Cu systems
. The results demonstrated the
rich chemistry and flexibility of these Nꢀcontaining ligands. Optimization of the system in
these studies led to multiple coordination compounds and low dimensional CPs with
interesting magnetic and catalytic properties, which were largely dependent on the unique
effects of the benzotriazole units in the coordination environment.
The next step in our studies was to combine this rewarding and flexible system with
I
the rich chemistry and unique coordination variety of Ag ions, exploring the resulting
structural aspects as well as potential catalytic applications to add to our existing findings.
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3
Having the superior alkynophilicity of Ag in mind, we identified the A multicomponent
coupling and the hydration of terminal alkynes as two potential reactions to test any afforded
compounds. The former reaction involves a coupling between an aldehyde, an amine and an
alkyne to generate propargylamines; these molecules are of significant importance in
synthetic chemistry, acting as intermediates towards biologically active compounds as well as
5
1–54
natural products
. The key mechanistic step during this reaction requires the formation of
a metal acetylide intermediate which is then added to the iminium ion. For this reason, a
I
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56
variety of Ag sources has been utilized in this reaction, including simple salts ,
57–60
41,42,61
coordination compounds
and CPs
. The second reaction involves treatment of
alkynes with water, resulting to the synthesis of ketones that follow Markonikov’s rule. As
the classic method for this reaction requires the addition of toxic mercury under harsh acidic
6
2
63
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conditions, multiple systems involving other transition metal elements (e.g Cu , Fe , Ru ,
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Au ) have also been explored. Another common strategy
involves incorporation of silver
as a coꢀcatalyst with gold to activate this reaction; on the other hand, only a few reports using
solely silver sources as catalysts can be found. The first example dates back to 2012, when
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Wagner and coꢀworkers employed AgSbF for the selective hydration of terminal alkynes.
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In the following years AgBF , AgOTf and a silver exchanged silicotungstic acid (STA)
4
72
catalyst were also tested successfully. However considerable disadvantages in these
procedures, such as the high loadings (up to 10 mol% in most cases) or temperatures, the use
of expensive salts (such as AgSbF
6
) or the lengthy workup for the preparation of the catalyst
(
in the case of AgSTA) reveal the need for further optimization in this area. In addition, no
silver coordination compounds have been reported to catalyze this reaction up to this date to
the best of our knowledge.
As a result of all the above, herein we report on two subsequently (interconnected)
1
subjects i) the synthesis and characterization of compounds [Ag(L )(CF
3
CO
2
)] (1),
1
T
2T
2T
[Ag (L ) (CF SO ) ]·2Me CO (2), [Ag(L )(ClO )(Me CO)] (3), [Ag(L )(BF )(Et O)] (4),
2
2
3
3 2
2
4
2
4
2
3
T
3
3T
3T
[
(
Ag (L ) (ClO ) ] (5), [Ag(L )(NO )] (6), [Ag (L ) (CF CO ) ] (7), [Ag (L )(CF SO ) ]
2
2
4 2 2
3
2
2
3
2 2
2
3
3 2
3T
8) and [Ag
2
(L )
2
(CF
3
CF
2
CO
2
)
2
2
]·2Me CO (9) and ii) the demonstration of the catalytic
3
activity of these compounds in the A coupling and alkyne hydration reactions.
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Scheme 1. The organic ligands L , L , and L used in this study.
EXPERIMENTAL
Materials. Chemicals (reagent grade) were purchased from Sigma Aldrich, Acros Organics
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3
and Alfa Aesar. Materials and solvents were used with no further purification. Ligands L – L
47
were synthesized according to the reported procedure . Safety note: Perchlorate salts are
potentially explosive; such compounds should be used in small quantities and handled with
caution and utmost care at all times. All crystallization experiments were performed in the
absence of light, although the resulting silver compounds do not appear to be light sensitive.
ꢀ1
Instrumentation. IR spectra of the samples were recorded over the range of 4000ꢀ650 cm
on a Perkin Elmer Spectrum One FTꢀIR spectrometer fitted with a UATR polarization
accessory. EIꢀMS was performed on a VG Autospec Fissions instrument (EI at 70 eV). TGA
analysis was performed on a TA Instruments Qꢀ50 model (TA, Surrey, UK) under nitrogen
and at a scan rate of 10°C/min. NMR spectra were measured on a Varian VNMRS solutionꢀ
state spectrometer at 30°C. Chemical shifts are quoted in parts per million (ppm). Coupling
constants (J) are recorded in Hertz (Hz).
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X-Ray crystallography. Data for L and compounds 1-5, 8 were collected (ωꢀscans) at the
University of Sussex, using either a Rigaku 007HF rotating anode generator with CCD plate
1
detector (for L , 1, 2) or an Agilent Xcalibur Eos Gemini Ultra diffractometer with CCD
plate detector (for 3ꢀ5, 8), under a flow of nitrogen gas at 173(2) K and Mo Kα (λ = 0.71073
Å) or Cu Kα radiation (λ = 1.54184 Å). CRYSALIS CCD and RED software was used
respectively for data collection and processing. Reflection intensities were corrected for
absorption by the multiꢀscan method. Data for 6, 7 and 9 were collected at the National
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Crystallography Service, University of Southampton. All structures were determined using
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77
Olex2 , solved using SHELXT
and refined with SHELXLꢀ2014 . All nonꢀH atoms were
refined with anisotropic thermal parameters, and Hꢀatoms were introduced at calculated
positions and allowed to ride on their carrier atoms. Crystal data and structure refinement
parameters for these compounds are given in Tables S1ꢀS2. Geometric/crystallographic
7
8
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calculations were performed using PLATON , Olex2 , and WINGX packages; graphics
7
9
were prepared with Crystal Maker and MERCURY . Each of the crystal structures has been
deposited at the CCDC 1851153ꢀ1851162.
SYNTHETIC PROCEDURES
3
General catalytic protocol for A coupling. A mixture of aldehyde (1 mmol), amine (1.1
mmol), alkyne (1.3 mmol), Ag catalyst (ca. 3 mg, 0.5 mol%, based on the aldehyde amount)
and 2ꢀpropanol (5 ml) was added into a sealed tube and stirred at 90 °C for appropriate time.
After completion of the reaction, the mixture was left to cool to room temperature, filtered
upon a short pad of silica (to separate the catalyst) and the filtrate was evaporated under
vacuum. The corresponding propargyl amine was isolated in pure form by column
chromatography using silica gel and a solvent mixture of hexane/EtOAc in a ratio from 10/1
to 5/1 as the eluent. The characterization data of the products matched well with those
49
reported in the literature .
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General catalytic protocol for alkyne hydration. A mixture of alkyne (1 mmol), water (150
ꢁl), Ag catalyst (18 mg, 3 mol%, based on the alkyne amount) and methanol (1.5 ml) was
added into a sealed tube and stirred at 90 °C for 24 hr. The mixture was then allowed to cool
to room temperature and filtered upon a short pad of silica (to withhold the catalyst). The
resulting residue was then loaded to a flash column chromatography using silica gel and the
corresponding ketone was isolated in pure form using a mixture of hexane/EtOAc in a ratio
from 10/1 to 3/1, as the eluent.
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Synthesis of [Ag(L )(CF
3 2
CO )] (1). 0.06 mmol (0.020 g) of L were dissolved in 17.5 ml
MeCN while stirring to produce a colorless solution. 0.12 mmol (0.027 g) of AgCF CO were
3
2
then added and the resulting white solution was filtrated and left undisturbed under room
ꢀ1
temperature to produce white needles after 12 days. Selected IR peaks (cm ): 3098 (w), 1691
(w), 1593 (w), 1497 (w), 1454 (w), 1310 (w), 1278 (w), 1226 (m), 1162 (w), 1114 (m), 1033
1
(
m), 825 (w), 780 (m), 738 (s), 621 (w). Yield: 36% (based on Ag). H NMR (600 MHz,
DMSOꢀd ) δ 8.02 (d, J = 8.3 Hz, 2H), 7.78 (d, J = 8.4 Hz, 2H), 7.49 (t, J = 7.7 Hz, 2H), 7.37
6
(
d, J = 7.8 Hz, 2H), 7.29 (s, 4H), 5.93 (s, 4H). Elemental Analysis for C H AgF N O : C
22 16 3 6 2
47.08, H 2.87, N 14.97; found C 47.01, H 2.81, N 15.08.
1T
1
Synthesis of [Ag
in 17.5 ml Me
AgOTf were then added. The resulting white solution was filtrated, then layered over nꢀ
2 2 3 3 2 2
(L ) (CF SO ) ]·2Me CO (2). 0.06 mmol (0.020 g) of L were dissolved
2
CO while stirring to produce a colorless solution. 0.12 mmol (0.031 g) of
ꢀ1
hexane in a 1:2 ratio. White needles were obtained after 8 days. Selected IR peaks (cm ):
3
8
404 (w), 1705 (w), 1574 (m), 1517 (w), 1421 (w), 1285 (m), 1234 (m), 1160 (m), 1026 (s),
1
66 (w), 795 (w), 747 (s), 635 (s). Yield: 32% (based on Ag). H NMR (600 MHz, DMSOꢀd
6
)
δ 8.03 (d, J = 8.0 Hz, 2H), 7.80 (d, J = 8.3 Hz, 2H), 7.50 (t, J = 7.2 Hz, 2H), 7.38 (t, J = 7.0
Hz, 2H), 7.30 (s, 4H), 5.94 (s, 4H). Elemental Analysis for C H Ag F N O S : C 43.98, H
48
44
2
6
12
8 2
3.38, N 12.82; found C 44.11, H 3.30, N 12.85.
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2
T
2
Synthesis of [Ag(L )(ClO
ml Me CO while stirring to produce a colorless solution. A solution containing 0.12 mmol
0.027 g) of AgClO in Me CO (10 ml) was slowly added. The resulting white solution was
filtrated, then layered over Et O in a 1:2 ratio. White needles were obtained after 4 days.
4 2
)(Me CO)] (3). 0.12 mmol (0.041 g) of L were dissolved in 10
2
(
4
2
2
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
ꢀ
1
Selected IR peaks (cm ): 1689 (m), 1594 (w), 1496 (w), 1455 (m), 1318 (m), 1286 (m), 1226
1
(
m), 1159 (w), 1084 (s), 818 (w), 780 (m), 750 (s), 622 (s). Yield: 81% (based on Ag). H
NMR (600 MHz, DMSOꢀd
6
) δ 8.02 (d, J = 8.4 Hz, 2H), 7.72 (d, J = 8.2 Hz, 2H), 7.46 (t, J =
7.5 Hz, 2H), 7.37 (dd, J = 16.6, 9.5 Hz, 3H), 7.31 (t, J = 7.6 Hz, 1H), 7.24 (d, J = 7.7 Hz,
2
H), 5.94 (s, 4H). Elemental Analysis for C H AgClN O : C 44.60, H 3.86, N 13.87; found
23 22 6 5
C 44.44, H 3.65, N 14.05.
2T
4 2
Synthesis of [Ag(L )(BF )(Et O)] (4). 4 was synthesized using the same method and ratios
4
as 3, with AgBF (0.023 g) as the metal salt. White needles were obtained after 3 days.
ꢀ
1
Selected IR peaks (cm ): 3098 (w), 1593 (w), 1497 (w), 1456 (w), 1310 (w), 1287 (w), 1226
(m), 1157 (w), 1055 (s), 1034 (s), 818 (w), 779 (m), 751 (s), 741 (s), 698 (w), 640 (w), 618
1
(
w). Yield: 79% (based on Ag). H NMR (600 MHz, DMSOꢀd ) δ 8.04 (d, J = 8.3 Hz, 2H),
6
7
.73 (d, J = 8.3 Hz, 2H), 7.47 (t, J = 7.6 Hz, 2H), 7.38 (dd, J = 16.0, 8.9 Hz, 3H), 7.33 (t, J =
15
7
.6 Hz, 1H), 7.25 (d, J = 7.5 Hz, 2H), 5.95 (s, 4H). N NMR (40 MHz, DMSOꢀd
6
) δ ꢀ155.99.
4 6
Elemental Analysis for C24H26AgBF N O: C 47.32, H 4.30, N 13.80; found C 44.59, H 3.70,
N 12.87. This result corresponds to the presence of two water molecules. Elemental Analysis
for (C H AgBF N O)(H O) : C 44.68, H 3.69, N 13.03.
24
26
4
6
2
2
3
T
3
Synthesis of [Ag
Me CO while stirring to produce a colorless solution. A solution containing 0.12 mmol
0.027 g) of AgClO in Me CO (10 ml) was slowly added. The resulting white solution was
filtrated, then left undisturbed under room temperature to produce white needles after 2 days.
2 2 4 2 2
(L ) (ClO ) ] (5). 0.12 mmol (0.041 g) of L were dissolved in 10 ml
2
(
4
2
ꢀ
1
Selected IR peaks (cm ): 1705 (w), 1594 (w), 1497 (w), 1457 (m), 1226 (m), 1153 (m), 1087
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5
5
6
(s), 1025 (m), 953 (w), 856 (w), 780 (m), 765 (m), 741 (s), 622 (s). Yield: 88% (based on
1
Ag). H NMR (500 MHz, DMSOꢀd
6
) δ 8.04 (d, J = 8.3 Hz, 2H), 7.88 (dd, J = 6.6, 3.2 Hz,
4
H), 7.71 (d, J = 8.4 Hz, 2H), 7.50 (t, J = 7.7 Hz, 2H), 7.45 – 7.37 (m, 6H), 7.36 – 7.20 (m,
H), 6.98 (d, J = 7.3 Hz, 2H), 6.24 (d, J = 4.8 Hz, 8H). These shifts indicate the presence of
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
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7
8
9
0
both isomer forms (1,1 and 1,2) in a 1:1 ratio. Elemental Analysis for C H Ag Cl N O : C
40
32
2
2
12
8
43.86, H 2.94, N 13.34; found C 43.78, H 2.85, N 13.37.
3
3
Synthesis of [Ag(L )(NO
3
)] (6). 0.06 mmol (0.020 g) of L were dissolved in 10 ml MeCN
while stirring to produce a colorless solution. After five minutes a solution containing 0.12
mmol (0.020 g) of AgNO in MeCN (10 ml) was slowly added. The resulting white solution
3
was filtrated, then layered over Et O in a 1:2 ratio. Colorless blocks were obtained after 1
2
ꢀ1
day. Selected IR peaks (cm ): 1592 (w), 1495 (w), 1455 (m), 1413 (m), 1290 (m), 1228 (m),
1161 (m), 1135 (w), 1113 (w), 1087 (w), 1033 (w), 1001 (w), 958 (w), 885 (w), 842 (w), 818
1
(
w), 767 (m), 759 (m), 748 (s), 708 (w), 667 (w), 625 (w). Yield: 82% (based on Ag). H
NMR (399 MHz, DMSOꢀd ) δ 8.09 (d, J = 8.4 Hz, 2H), 7.78 (d, J = 8.3 Hz, 2H), 7.54 (t, J =
6
7.6 Hz, 2H), 7.44 (t, J = 7.5 Hz, 2H), 7.28 – 7.21 (m, 2H), 6.96 – 6.89 (m, 2H), 6.27 (s, 4H).
15
N NMR (40 MHz, DMSOꢀd
6 7 3
) δ ꢀ154.37. Elemental Analysis for C20H16AgN O : C 47.08,
H 3.16, N 19.22; found C 47.18, H 3.25, N 19.33.
3
T
3
2 2 3 2 2
Synthesis of [Ag (L ) (CF CO ) ] (7). 0.06 mmol (0.020 g) of L were dissolved in 10 ml
Me CO while stirring to produce a colorless solution. A solution containing 0.12 mmol
2
(0.027 g) of AgCF CO in Me CO (10 ml) was slowly added. The resulting white solution
3
2
2
was filtrated, then layered over nꢀhexane in a 1:2 ratio. White needles were obtained after 2
ꢀ1
days. Selected IR peaks (cm ): 1665 (w), 1595 (w), 1499 (w), 1457 (m), 1222 (s), 1147 (s),
1
1
025 (s), 952 (w), 837 (w), 780 (m), 746 (s), 633 (s). Yield: 52% (based on Ag). H NMR
(
600 MHz, DMSOꢀd ) δ 8.09 (d, J = 8.5 Hz, 1H), 8.06 (d, J = 8.6 Hz, 1H), 7.92 – 7.86 (m,
6
2H), 7.79 (d, J = 8.4 Hz, 1H), 7.75 (d, J = 8.4 Hz, 1H), 7.57 – 7.48 (m, 3H), 7.46 – 7.37 (m,
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5H), 7.34 – 7.21 (m, 5H), 6.97 (d, J = 7.5 Hz, 1H), 6.94 – 6.89 (m, 2H), 6.28 –6.26 (m, 8H).
These shifts indicate the presence of both isomer forms (1,1 and 1,2) in a 1:1 ratio. Elemental
Analysis for C44
2 6 12 4
H32Ag F N O : C 47.08, H 2.87, N 14.97; found C 47.00, H 2.84, N 15.06.
3T
Synthesis of [Ag (L )(CF SO ) ] (8). A procedure similar to the synthesis of 7 was
2
3
3 2
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
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3
3
3
4
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4
4
4
4
4
4
4
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5
5
5
5
5
5
5
6
0
1
2
3
4
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6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
followed, using AgOTf (0.12 mmol, 0.031 g) as the metal salt. White needles were obtained
ꢀ1
after 1 day. Selected IR peaks (cm ): 1594 (w), 1498 (w), 1458 (m), 1265 (s), 1241 (s), 1223
(s), 1166 (m), 1023 (s), 956 (w), 861 (w), 766 (w), 751 (s), 740 (s), 629 (s), 606 (w). Yield:
1
58% (based on Ag). H NMR (600 MHz, DMSOꢀd
6
) δ 8.08 (d, J = 8.4 Hz, 2H), 8.05 (d, J =
8
7
5
.4 Hz, 1H), 7.90 – 7.85 (m, 2H), 7.79 (d, J = 8.4 Hz, 2H), 7.76 (d, J = 8.4 Hz, 1H), 7.58 –
.49 (m, 3H), 7.46 – 7.38 (m, 3H), 7.34 – 7.21 (m, 3H), 6.99 (d, J = 7.5 Hz, 1H), 6.94 (dd, J =
.6, 3.5 Hz, 2H), 6.27 (s, 6H). These shifts indicate the presence of both isomer forms (1,1
2 6 6 6 2
and 1,2) in a 2:1 ratio. Elemental Analysis for C22H16Ag F N O S : C 30.93, H 1.89, N 9.84;
found C 31.10, H 2.01, N 9.86.
3
T
Synthesis of [Ag (L ) (CF CF CO ) ]·2Me CO(9). A procedure similar to the synthesis of 7
2
2
3
2
2 2
2
was followed, using AgCF CF CO (0.12 mmol, 0.033 g) as the metal salt. White needles
3
2
2
ꢀ1
were obtained after 3 days. Selected IR peaks (cm ):1661 (m), 1499 (w), 1455 (w), 1319 (m),
1277 (w), 1212 (m), 1166 (m), 1147 (m), 1022 (m), 852 (w), 815 (w), 771 (w), 747 (s), 728
1
(
s), 628 (w). Yield: 64% (based on Ag). H NMR (600 MHz, DMSOꢀd
6
) δ 8.05 (d, J = 8.4 Hz,
2H), 7.90 (dd, J = 6.6, 3.1 Hz, 4H), 7.74 (d, J = 8.4 Hz, 2H), 7.50 (t, J = 7.7 Hz, 2H), 7.43
(dd, J = 6.6, 3.0 Hz, 4H), 7.39 (t, J = 7.7 Hz, 2H), 7.34 – 7.20 (m, 6H), 6.95 (d, J = 7.5 Hz,
H), 6.28 (s, 4H), 6.26 (s, 4H). These shifts indicate the presence of both isomer forms (1,1
2
2 10 12 5
and 1,2) in a 1:1 ratio. Elemental Analysis for C49H38Ag F N O : C 45.96, H 2.99, N 13.12;
found C 45.97, H 3.06, N 13.20.
CRYSTAL STRUCTURE DESCRIPTION
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1
Compound 1 was synthesized using silver trifluoroacetate and the paraꢀsubstituted L
ꢁ
ligand. The structure crystallizes in the triclinic ꢀ1 space group and its asymmetric unit
I
1
consists of one Ag center, one L molecule and one trifluoroacetate anion. In this
1
coordination mode, L adopts a chair conformation, with the benzotriazole units being
0
1
2
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5
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7
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0
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0
I
parallel to each other. Each ligand molecule coordinates to a total of two Ag centers as seen
in Scheme 2, mode A. The trifluoroacetate anions also act as bridging ligands, generating
1
[Ag (L ) (CF CO ) ] nodes which expand to a two dimensional architecture. As a result, 1
2
4
3
2 2
may be described as a 2D coordination polymer that propagates along the a0c plane (Figure
2 2
, left). Each of the metal centers possesses a tetrahedral geometry and a {N O }
1
coordination environment. This tetrahedron is rather distorted, with the relevant angles
ranging from 97.18(18) to 140.94(19)°. The related AgꢀN and AgꢀO bond distances are
surprisingly similar, ranging from 2.304(5) to 2.340(5) Å. No hydrogen bonds or other
supramolecular interactions were observed.
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9
0
1
2
3
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5
6
7
8
9
0
Figure 1. (up) Part of the twoꢀdimensional framework along the a0c plane in compound 1. H
atoms are omitted for clarity. (down) Part of the twoꢀdimensional framework along the b0c
plane in compound 2. For clarity, H atoms, solvent molecules and part of the triflate anions
have been omitted. Color code Ag (anthracite), C (light grey), N (light blue), O (red), F (light
green).
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Compound 2 was synthesized through the use of silver triflate as the metal salt and
the resulting structure crystallizes in the monoclinic P2
1
space group. In this case, an
1
isomerism phenomenon is observed in the benzotriazole moieties of all L molecules, as one
of the two –CH linkers connects to the middle N atom of the benzotriazole. Consequently,
2
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1T
the disubstituted 1,2ꢀyl analogue (L ) is obtained, instead of the 1,1ꢀyl. As a result the
I
1T
asymmetric unit of 2 contains two Ag centers, two L molecules, two triflate anion
molecules that act as terminal ligands and two acetone lattice solvents. The latter will not be
further mentioned in this description. The coordination mode for the two crystallographically
1
T
independent L molecules (Scheme 2, Modes B and C) is similar, as each of the ligands
I
coordinates to three different Ag centers. More specifically, the benzotriazolꢀ1ꢀyl unit
I
coordinates to one Ag center through the single far nitrogen atom, while the 2ꢀyl moiety
1
T
coordinates to two metal centers through its two far nitrogen atoms. The two L molecules
however differ slightly in orientation as the angle between their benzotriazole entities are
49.27(3) and 43.47(3)° respectively. This conformation accounts for the formation of
1
T
[
Ag (L ) (CF SO ) ] nodes which are connected to each other through AgꢀN bonding to
2 2 3 3 2
generate the resulting twoꢀdimensional coordination polymer along the b0c plane (Figure 1,
I
right). Each Ag center possesses a {N
3
O} coordination environment and a slightly distorted
tetrahedral geometry. The AgꢀN bonds range from 2.266(10) to 2.349(10) Å, while the AgꢀO
are slightly larger at 2.323(15) and 2.366(9) Å. The angles of the tetrahedra range from
97.2(3) to 135.0(3)°. While no strong Hꢀbonds are formed, π⋯π interactions form between
the benzene and the benzotriazole moieties of ligand molecules to further stabilize the two
dimensional architecture. The parameters for these interactions are detailed in Table S3.
2
For the construction of compound 3 the metaꢀsubstituted ligand L was utilized along
1
with silver perchlorate. The complex crystallizes in the monoclinic P2 /n space group and
I
contains one Ag center, a ligand molecule, a perchlorate anion as well as one acetone
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molecule in the asymmetric unit. Interestingly, another case of ligand isomerism is observed
2
T
as the ligand molecule appears as the 1,2ꢀdisubstituted benzotriazole analogue (L ). Each of
2
T
I
these L ligands coordinates to two different Ag centers through the far N atom of each
benzotriazole moiety. Due to the increased flexibility of the –CH2 linkers, in this
conformation mode (Scheme 2, Mode D) the planes of the two benzotriazole moieties are
found at an angle of 54.56(19)°. As a result of these features, the structure of 3 consists of a
oneꢀdimensional polymeric chain which propagates along the b axis (Figure 2, upper). The
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
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3
3
3
3
3
3
3
4
4
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4
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4
4
4
5
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5
5
5
5
5
6
0
1
2
3
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5
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7
8
9
0
1
2
3
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5
6
7
8
9
0
1
2
3
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6
7
8
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1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
I
perchlorate and acetone molecules also coordinate to the Ag center, which exhibits a heavily
distorted tetrahedral geometry in a {N O } coordination environment. As expected, the AgꢀO
2
2
bond distances, ranging from 2.47520(8) to 2.52007(9) Å, are significantly larger than the
analogous AgꢀN values which were calculated at 2.15565(8) and 2.18819(7) Å respectively.
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0
Figure 2. (up) Part of the oneꢀdimensional framework in 3. H atoms are omitted for clarity.
(down) Part of the oneꢀdimensional framework in 4 along the b axis. H atoms are omitted for
clarity. Color code Ag (anthracite), C (light grey), N (light blue), B (dark grey), F/Cl (light
green).
1
Compound 4 was found to crystallize in the monoclinic P2 /n space group.
Determination of the structure through XꢀRay crystallography reveals a similar case of
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2T
isomerization of L to L as seen in 3. However, in this case the ligand shows a different
conformation (Scheme 2, Mode E), as the two benzotriazole moieties are almost parallel to
each other at an angle of only 3.70(11)°. Due to this, the compound propagates in one
direction, forming 1D helixꢀlike chains along the b axis as shown in Figure 2, lower. This
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
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7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
T
difference in the conformation of L also accounts for significant variance in AgꢀAg
I
distance; this value was measured at 8.9893(4) Å in 3 and 10.3143(9) Å in 4. Each Ag center
is coordinated to four atoms in a distorted tetrahedral geometry. The coordination
2
T
environment consists of two N atoms from two L molecules, one F atom from
tetrafluoroborate anions and one O atom from a coordinating diethyl ether solvent molecule.
The largest bond in this coordination sphere is the AgꢀF distance which was measured at
2
.615(4) Å. In contrast, the AgꢀN bond values were the smallest at 2.224(5) and 2.250(4) Å.
The arrangement of the framework also promotes the formation of interꢀmolecular π···π
8
0
interactions which account for further stability. These weak interactions occur between
certain benzotriazole aromatic rings, as detailed in Table S4.
ꢁ
Compound 5 crystallizes in the triclinic ꢀ1space group and its structure consists of
3T
2 2 4 2
two crystallographically independent dimeric [Ag (L ) (ClO ) ] units as shown in Figure 3.
Similarly to the paraꢀ and metaꢀ analogues, the orthoꢀsubstituted ligand also appears here as
3
T
the L isomer. The presence of two different types of dimeric units within the structure are
3
T
due to the coordination modes and conformations of L (Scheme 2, Modes F and G). In the
I
first unit the benzotriazolꢀ1ꢀyl moiety coordinates to both Ag centers through the respective
middle and far nitrogen atoms; the related atoms appear aligned in a single plane. The 2ꢀyl
moiety is found at an angle of 63.31(9)° to this plane and coordinates to only one metal
I
center. As a result, the relevant Ag centers possess a distorted tetrahedral {N
3
O}
3
T
environment. In contrast, the second dimer consists of L ligands in which the benzotriazole
entities are almost parallel (6.02(8)° angle between the two planes). This dimeric component
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7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
is further stabilized by a weak Ag···π interaction which is formed as the phenyl group of the
ligand backbone faces towards the silver atom with a slight slippage of 1.717 Å, as depicted
in Scheme S1. The centroidꢀmetal distance in this case was measured at 3.177(2) Å. A series
of relevant Ag···C distances from 2.737(5) to 3.317(5) further support the formation of this
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
I
interaction. Each of these units coordinate to one Ag center through their respective far
nitrogen atoms and therefore the metal ions show a distorted trigonal geometry and a {N O}
2
coordination environment. The formation of several intermolecular π···π interactions (Table
S5) further stabilizes the packing arrangement of these dimeric units.
Figure 3. The two crystallographically independent dimeric units in 5. H atoms are omitted
for clarity. Color code Ag (anthracite), C (light grey), N (light blue), O (red), Cl (light green).
Crystallographic analysis for compound 6 reveals a oneꢀdimensional polymeric
structure which extends along the b axis to form a ribbonꢀlike 1D framework with small
ꢁ
voids (Figure4, left). The compound crystallizes in the triclinicꢂꢀ1 space group and its
I
3
asymmetric unit contains an Ag center, one L ligand molecule and one nitrate anion which
acts as a bridging ligand. Interestingly, no isomerization of the ligand is observed: each of the
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8
9
I
benzotriazolꢀ1ꢀyl moieties coordinate to one Ag ion through the far nitrogen atom (Scheme
2, Mode H), with the respective AgꢀAg distance at 10.749(3) Å. In regards to the ligated
nitrate anion, one oxygen atom coordinates to the metal ion, while another oxygen
I
coordinates to the same Ag center as well as a symmetry related one. As a result, two zigꢀzag
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
D architectures are bridged by the nitrate anions to form the resulting ribbonꢀlike
framework. The resulting {N O } coordination environment of the metal ion provides a
2
3
8
1
distorted square pyramidal geometry (τ = 0.05 ). As expected, the mean AgꢀN distances
(2.242(7) and 2.243(6) Å) are significantly shorter than the respective AgꢀO distances
(ranging from 2.512(6) to 2.720(6) Å).
Figure 4. (left) Part of the oneꢀdimensional framework in 6 along the b axis. H atoms are
omitted for clarity. Color code Ag (anthracite), C (light grey), N (light blue), O (red). (right)
The structure of compound 7. H atoms are omitted for clarity. Color code Ag (anthracite), C
(light grey), N (light blue), O (red), F (green).
Compounds 7 and 9 contain isoskeletal cores and as such only the former will be
3
T
described in detail. The structure of 7 consists of a wheelꢀlike [Ag (L ) (CF CO ) ] dimeric
2
2
3
2 2
3
T
unit in which the ligand appears as the L isomer (Figure 4, right). Similarly to one of the
dimers in compound 5, the benzotriazole moieties in the ligand are found almost parallel to
I
each other at an angle of 7.97(8)° and coordinate to a total of two Ag ions through their
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8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
respective far nitrogen atoms(Scheme 2, Mode I). This AgꢀAg distance was measured at
3.9108(7) Å. A trifluoroacetate anion also coordinates to the metal center through one oxygen
2
atom to complete its {N O} coordination sphere. The relevant angles in this trigonal
geometry range from 105.18(13)° to 127.82(11)°. Intermolecular π···π interactions provide
extended stability to this architecture. The parameters for these interactions may be found at
Table S6.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
Finally, compound 8 crystallizes in the monoclinic P2 /n space group and its
I
asymmetric unit contains two Ag centers, two triflate anion molecules and one organic
3
T
ligand as the L isomer. The conformation of the latter is similar to other compounds
mentioned in this study, with the planes of the benzotriazole entities forming a very small
angle of 12.18(12)°. However, the coordination mode varies in this case, as the benzotriazolꢀ
2ꢀyl unit utilize both far nitrogen atoms to coordinate to two metal centers (Scheme 2, Mode
J). The ligated triflates also play an important role in the resulting architecture as they bridge
3
T
symmetry related [Ag (L ) ] nodes. This bridging leads to the formation of a twoꢀ
2
2
dimensional sheet along the b0c plane (Figure 5) which is supported by argentophilic
I
interactions between two symmetryꢀrelated Ag centers which are found at a distance of
3.1794(11) Å. Further support is provided by the formation of week π···π interactions
between aromatic rings as detailed in Table S7.It is worth noting that each of the triflate units
bridge the aforementioned nodes in a different way (Scheme 2, bottom middle and right). For
I
the first triflate, each of the three oxygen atoms coordinate to different Ag ions, while the
second anion employs only one oxygen atom for coordination, binding concurrently to the
I
two Ag centers which participate in the argentophilic interaction. As a result of all the above,
the two crystallographically independent metal centers of this compound possess a distorted
8
1
trigonal bipyramidal (τ = 0.68 ) coordination geometry, respectively.
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8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 5. Part of the twoꢀdimensional framework along the b0c plane in compound 8. H
atoms are omitted for clarity. Color code Ag (anthracite), C (light grey), N (light blue), O
(red), F (green), S (yellow).
Table 1. Structural summary of compounds 1ꢀ13.
Entry Compound Ligand
Coordination
Solvent
MeCN
Metal salt
Dimensionality
Environment of
I
M (Ag )
1
1
2
3
4
5
1
2
3
4
5
L
AgCF
3
CO
2
2D
2D
1D
1D
0D
1T
L
Me
2
CO
3 3
AgCF SO
2
T
L
L
L
Me CO
AgClO4
2
2T
Me
Me
2
CO
CO
AgBF
4
3
T
2
AgClO
4
3
6
6
L
MeCN
AgNO
3
1D
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8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
3
3
T
T
7
8
7
8
L
Me CO
AgCF CO2
0D
2D
2
3
L
Me CO
AgCF SO3
2
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
T
9
9
L
Me
2
CO AgCF
3
CF
2
CO
2
0D
Ag
Ag
N
Ag
Ag
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Ag
Ag
N
Ag
M
N
N
Mode A
Mode B
(Compound 2)
Mode C
Compound 2)
(Compound 1)
(
N
N
Ag
N
N
N
N
Ag
N
N
N
N
N
N
N
N
N
N
N
Ag
N
Ag
Ag
Ag
Mode F
Mode D
(Compound 3)
Mode E
(Compound 4)
(Compound 5)
Ag
Ag
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Ag
N
Ag
N
N
N
Ag
Ag
Mode G
Compound 5)
Mode H
(Compound 6)
Mode I
(Compounds 7, 9)
(
Ag
N
N
N
N
N
N
Ag
Mode J
Compound 8)
Ag
(
Scheme 2. (Modes AꢀJ) The coordination modes for all ligands that appear in compounds 1ꢀ
8
2
9
. (bottom middle and right) The coordination modes of the triflate anions in compound 8.
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7
8
9
Characterization of compounds.
Thermogravimetric Analysis. TGA measurements were conducted for all compounds to
examine their thermal stability. The results illustrate this behavior in the region of 50ꢀ
1000°C. These experiments revealed similar outcomes, as in all cases the main (polymeric or
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
dimeric) core retains its stability up to the region of ~220ꢀ300°C, where gradual
decomposition begins to take place. Complex 1 shows a gradual mass loss in the 50ꢀ250°C
range which is due to the removal of trifluoroacetate entities (calcd.: 20.45%, theor.:
20.18%). Almost immediately, the core is subjected to further gradual decomposition towards
the final oxide (calcd.: 58.77%, theor.: 59.30%). In the case of complex 2, the first mass loss
(9.59%) occurs from 50 to 114°C and corresponds to the loss of the acetone lattice molecule
in good agreement (theoretical value: 8.87%). The remaining core is stable until 291°C,
where it collapses towards gradual decomposition. In compound 3, the main core retains its
2
stability until 297°C where it is decomposed to Ag O. The calculated (79.24%) and
theoretical (78.96%) values are also in very good agreement. Compound 4 remains relatively
stable until the region of 285°C (as the Et O molecule is lost before the TGA measurement
2
begins) and the first mass loss corresponds to the collapse of the entire framework until
decomposition (calcd.:= 82.94%,theor.: 81.14%). Complex 5 shows very similar thermal
stability, retaining its main core up to 285°C before eventual collapse. In compound 6, an
initial mass loss of 11.60% occurs at approximately 273°C and finishes at 286°C, attributed
to the loss of the nitrate anion (theor.: 12.15%). Decomposition of the remaining framework
takes place almost immediately (calcd.: 65.65%, theor.: 65.33%). The structure of 7 remains
relatively stable up to the region of 215°C, where a large mass loss occurs (81.73%),
attributed to the collapse of the framework with reasonable agreement (theor: 79.48%). In
complex 8, there is initially a removal of the triflate anions (28.11% mass loss) from the
framework which begins at 275°C and concludes at 310°C. Shortly after this point, the
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9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
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5
5
5
5
5
5
5
6
remaining structure collapses to eventual decomposition to silver oxide (calcd.: 54.58%,
theor.:55.59%). Finally, in compound 9 the first mass loss occurs until approximately 218°C
and corresponds to the loss of the acetone lattice solvent molecule (calcd: 4.54%, theor:
5.96%). The second mass loss begins almost immediately (at the region of 220°C) and is
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
owed to the collapse of the remaining compound up to decomposition (82.16% mass loss)
with satisfactory agreement to the theoretical value (84.26%). The respective TGA graphs are
presented in the Supporting Information (Figures S13ꢀS21).
ESI-MS studies. Electrospray ionization mass spectrometry (ESIꢀMS) in methanolic solution
was also performed for compounds 1ꢀ9, to further verify their behavior. The resulting spectra
are very similar for all complexes, with two peaks at 447.05 and 789.20 m/z which
+
+
2
correspond to the relevant [AgL] and [AgL ] fragments. These are the main peaks at all
compounds with the exception of complex 6; in this case, the main peaks correspond to
ligandꢀbased fragments and the aforementioned Agꢀcontaining peaks are found in very low
intensity, indicating that the polymer may not be so stable in solution. Several of the
+
remaining compounds present additional peaks and the most common fragment is [Ag
2
L
2
X] ,
where X is the relevant anion in each case. Other peaks that are present in some compounds
+
+
+
+
correspond perfectly to the [AgL
3 2 3 3 2 2 3 2
] , [Ag L X] , [Ag L X ] and [AgL X ] fragments. All
spectra are presented in Figures S22ꢀS30 along with a detailed analysis of the fragments.
83,84
Isomerism effect and NMR studies. The tautomerism of heterocycles
is a very common
8
5–89
phenomenon that has been extensively studied for several decades. Related reports
focusing specifically on benzotriazole and its derivatives began surfacing especially after the
90–94
1980s, including studies on relevant metal complexes
. Multiple efforts have documented
that several types of substituted benzotriazole derivatives exist in solution as an equilibrium
9
5–98
mixture of the corresponding 1ꢀ and 2ꢀisomers
. Some of these cases include Nꢀ
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100,101
102
arylmethylꢀ , Nꢀ(aminomethyl)ꢀ
, Nꢀ(alkoxyalkyl)ꢀ
and Nꢀ(alkylthioalkyl)ꢀ or Nꢀ
103
83,86,95
(arylthioalkyl)ꢀbenzotriazoles . It has been shown
that the main parameters that affect
the position of this equilibrium are i) solvent polarity, as a more polar solvent shifts the
equilibrium towards the more polar 1ꢀisomer, ii) temperature, as benzotriazole has been
found to be stable as the 2ꢀisomer in gas phase, and iii) the nature of the substituent, as the
ratio of the 2ꢀisomer increases in equilibrium when the bulkiness of the substituent is also
increased. Interestingly, a search in the literature reveals no similar investigations for bisꢀ
benzotriazole substituted compounds. The present report contains several compounds with
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
I
both isomer forms in three different bisꢀbenzotriazole ligands, while the presence of Ag
allows for possible NMR studies. We therefore felt this was an excellent opportunity to shed
I
more light into this isomerism effect. The sole reported Ag compound with these ligands is a
2
104
dimeric [Ag
2
(L )
3
](NO
3
)
2
·(MeCN)·compound as described by O’Keefe and Steel , in which
2
only the 1,1ꢀisomer form of L is present in the crystal structure; unfortunately, no NMR
studies were performed for the compound in that report.
We first established purity during the synthesis by obtaining crystals of the 1,1ꢀisomer
1
3
1
form for ligands L ꢀL . Crystals of compounds 1ꢀ9 were then characterized with HNMR in
deuterated DMSO, as none of the complexes was soluble in CDCl . The obtained ppm shifts
3
reveal interesting results: In general, the 1,1ꢀisomer form exists almost solely (>99:1 ratio) in
solution for compounds 1 and 6 results that is consistent with that determined in the crystal
structure. Surprisingly, the corresponding 1,1ꢀisomers were also obtained for compounds 2ꢀ4,
despite the exclusive presence of the 1,2ꢀisomers in their crystal structures. On the other
hand, both 1,1ꢀ and 1,2ꢀ isomers are present in the solution form for complexes 5, 7, 8 and 9
with various ratios (1:1, 1:1, 2:1 and 1:1 respectively). These results demonstrate that the 1,1ꢀ
form is generally dominant in solution even in cases where the crystal structure does not
contain this tautomer; however, the equilibrium may still move towards the 1,2ꢀform in some
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1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
cases. Having in mind that all NMR studies were performed under the same solvent and
temperature conditions, it can be proposed that the main reason for the presence of the 1,2ꢀ
isomer is the nature of the substitution. This hypothesis is consistent with our findings for
compounds 5, 7ꢀ9 where the used substituent is increasing its bulky effect and the
benzotriazole units are found in the orthoꢀposition. From the crystal structure of these
compounds it is evident that the orthoꢀsubstitution accounts for larger steric effects compared
to the paraꢀ and metaꢀsubstituted structures. Additional intermolecular π···π and
argentophilic interactions are also present in these complexes, possibly hindering the
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
5
equilibrium shift to the 1,1ꢀform even further. N HMBC studies (Figures S40ꢀS41) were
also performed for selected compounds 4 and 6. Both spectra show only a single resonance,
originating from the ꢀCH
the triazole. The respective N chemical shifts (referenced to CH
154.37 (for 6) ppm are also consistent with a pyrroleꢀlike nitrogen, suggesting the existence
of 1,1ꢀisomer in both compounds.
2
linker, showing a 2JNH correlation to the pyrroleꢀlike nitrogen of
1
5
3
2
NO ) at ꢀ155.99 (for 4) and
ꢀ
On the other hand, less clear conclusions may be drawn in regards to the parameters
which promote the presence of the 1,2ꢀisomer in the solid state. Synthetic conditions such as
the temperature, metal:ligand ratio or crystallization method do not seem to have any
noticeable effect. However, a correlation with the solvent choice and polarity during the
initial synthesis may be proposed, as all 1,1ꢀbased compounds were afforded in acetonitrile
(ꢁ = 3.92 D), while the use of the slightly less polar acetone (ꢁ = 2.88 D) resulted only in 1,2ꢀ
based compounds. Interestingly, this pattern is additionally supported by two more
compounds synthesized during our experiments, which are not presented in detail due to very
2
weak crystallographic data. Both of these compounds, formulated as [Ag(L )(CF
3
CF
2
CO
2
)]
2
and [Ag (L ) ](ClO ) (Figures S2ꢀS3), were synthesized in acetonitrile and contain only the
2
3
4 2
1,1ꢀisomer of the ligand. A comparison between the latter complex and compound
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Crystal Growth & Design
1
2
3
4
5
6
7
8
9
2
T
[Ag(L )(ClO
role. Moreover, the [Ag
However, this phenomenon is only consistent for Ag complexes, as several Cu and Co
4
)(Me
2
CO)](3) show that the choice of solvent could indeed play an important
2
104
2
3 3 2
(L ) ](NO ) (MeCN)·compound was recrystallized in acetonitrile.
I
II
II
compounds reported by us in previous studies did not exhibit similar behavior. As such, more
studies are required to fully comprehend this effect.
Catalytic studies
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
A coupling reaction. To initiate our investigations for the catalytic potential of 1ꢀ9 we first
3
employed them in the multicomponent A coupling of benzaldehyde, pyrrolidine and
phenylacetylene, performing an extensive screening of all related parameters as seen in Table
2
2
. All compounds proved to be ineffective in solvents such as water, DMF and DMSO (Table
, entries 7 – 9, 23 – 25), however they provided low yields in the homogeneous catalysis of
the reaction when other common organic solvents were used such as Toluene, THF, CH
CH Cl and CHCl (Table 2, entries 6, 10 – 13, 22, 26 – 29). In general, the highest yields
were achieved through the use of polar alcoholic solvents and especially with the
3
CN,
2
2
3
1
05
environmentally friendly solvent
2ꢀpropanol (iPrOH) when the reaction mixture was
o
heated to 90 C for 12 hours. All compounds were found to catalyze the reaction under these
conditions (Table 2, entries 4ꢀ5, 14ꢀ15, 19ꢀ21, 32ꢀ36); amongst these, the 1D CP 4 afforded
the corresponding product at excellent yields of 94%, with very low loadings of 0.5 mol%
ꢀ1
used (TOF = 188 and TON = 15.7 hr , calculated with the ratio of product mol/catalyst mol).
I
To further evaluate the efficiency of 4, we compared the performances of all reported Ag
sources which have been tested in the model reaction to the best of our knowledge, including
simple salts, coordination polymers and coordination compounds (Table S8). To our delight,
4
emerges as a highly advantageous catalyst in many aspects, due to the resulting excellent
yield and TOF number which outperforms many of the reported Ag sources (Table S8,
entries 1ꢀ8). On the other hand, the stirring times in the case of our catalyst appear to be
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Page 28 of 51
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
4
1,42,56,57,60,106
longer than those usually reported
. Despite this, the conditions of our proposed
2
reaction system appear to be less harsh or tedious (e.g. no N atmosphere or environmentally
I
unfriendly solvent is needed). Various Ag salts were also tested under the same conditions
(
Table S8, entries 10ꢀ15) showing slightly inferior performance, further indicating the
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
superiority of 4.
Table 2. Optimization of the conditions for the synthesis of propargylamines.
a
b
ꢀ1
Entry
Catalyst (mol%)
Solvent
MeOH
EtOH
Yield (%)
TON
TOF (hr )
1
2
3
4
5
6
7
8
9
1 (2)
trace
18
ꢀ
9
ꢀ
0.8
1.2
3.6
13.8
0.6
ꢀ
1 (2)
1 (2)
iPrOH
28
14
43
166
7
c
1 (2)
iPrOH
85
c
1 (0.5)
1 (2)
iPrOH
83
Toluene
14
d
1 (2)
H
O
NR
ꢀ
2
d
1 (2)
DMF
DMSO
THF
NR
ꢀ
ꢀ
d
1 (2)
NR
ꢀ
ꢀ
10
1 (2)
10
13
5
0.4
0.6
11
1 (2)
MeCN
7
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Crystal Growth & Design
1
2
3
4
5
6
7
8
9
12
1 (2)
1 (2)
2 (0.5)
3 (0.5)
4 (2)
4 (2)
4 (2)
4 (2)
4 (1)
4 (0.5)
4 (2)
4 (2)
4 (2)
4 (2)
4 (2)
4 (2)
4 (2)
4 (2)
CH
2
Cl
2
11
14
81
88
<10
16
29
95
94
94
18
6
7
0.5
0.6
13.5
14.7
ꢀ
13
14
15
CHCl
iPrOH
iPrOH
3
c
162
176
ꢀ
c
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
16
MeOH
EtOH
17
18
19
20
8
0.7
1.3
4
iPrOH
15
48
94
188
9
c
iPrOH
c
iPrOH
7.8
15.7
0.8
ꢀ
c
21
iPrOH
22
23
24
Toluene
d
H
2
O
NR
ꢀ
d
DMF
DMSO
THF
NR
ꢀ
ꢀ
d
25
NR
ꢀ
ꢀ
26
27
28
29
<10
11
15
16
63
94
70
81
66
71
74
ꢀ
ꢀ
MeCN
6
0.5
0.7
0.7
21
CH
2
Cl
2
8
CHCl
iPrOH
iPrOH
iPrOH
iPrOH
iPrOH
iPrOH
iPrOH
iPrOH
3
8
e
c
c
c
c
c
c
c
c
30
4 (0.5)
126
188
140
162
132
142
148
ꢀ
f
3
3
3
1
2
3
4 (0.5)
7.8
11.7
13.5
11
5 (0.5)
6 (0.5)
34
7 (0.5)
3
3
3
5
6
7
8 (0.5)
11.8
12.3
ꢀ
9 (0.5)
d
No catalyst
NR
a
Reaction conditions: benzaldehyde (25 ꢁL, 0.25 mmol), pyrrolidine (22 ꢁL, 0.275 mmol),
phenylacetylene (43 ꢁL, 0.4 mmol), catalyst (mol% based on aldehyde amount), solvent (3
b
c
o
d
e
ml), 12 hr stirring, air. Isolated yields based on aldehyde. T = 90 C. No reaction. under
f
6
hrs stirring. under 24 hrs stirring.
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