Gold(I) complexes bearing ring-fused benzoxazine-derived triazolylidenes and their use in C–N bond-forming processes

Article abstract of DOI:10.1002/aoc.6098

We report the synthesis and full characterization of a novel series of ring-fused benzoxazine-derived triazolium salts (1a–c) and their corresponding triazolylidene gold(I) complexes (2a–c). All new compounds were fully characterized by means of ¹H and ¹³C NMR spectroscopy, elemental analyses, and mass spectroscopy and in the case of triazoliums 1a and 1b by single-crystal X-ray diffraction. The new triazolylidene gold complexes (2a–c) were tested as precatalysts in the hydroamination and hydrohydrazination of terminal alkynes employing aniline derivatives and hydrazine as nitrogen sources, respectively.

Full text of DOI:10.1002/aoc.6098

Received: 24 August 2020
DOI: 10.1002/aoc.6098
Revised: 5 October 2020
Accepted: 29 October 2020
F U L L P A P E R
Gold(I) complexes bearing ring-fused benzoxazine-derived
triazolylidenes and their use in C–N bond-forming
processes
Emmanuel Campos-Dominguez | Jose Vasquez-Perez | Susana Rojas-Lima |
Heraclio Lopez-Ruiz | Daniel Mendoza-Espinosa
ꢀ
Area Académica de Química, Universidad
We report the synthesis and full characterization of a novel series of ring-fused
benzoxazine-derived triazolium salts (1a–c) and their corresponding
triazolylidene gold(I) complexes (2a–c). All new compounds were fully charac-
Autónoma del Estado de Hidalgo, Mineral
de la Reforma, Hidalgo, Mexico
Correspondence
1
terized by means of H and 13C NMR spectroscopy, elemental analyses, and
ꢀ
Daniel Mendoza-Espinosa, Area
Académica de Química, Universidad
Autónoma del Estado de Hidalgo,
mass spectroscopy and in the case of triazoliums 1a and 1b by single-crystal
X-ray diffraction. The new triazolylidene gold complexes (2a–c) were tested as
precatalysts in the hydroamination and hydrohydrazination of terminal
alkynes employing aniline derivatives and hydrazine as nitrogen sources,
respectively.
Carretera Pachuca-Tulancingo Km. 4.5,
Mineral de la Reforma, Hidalgo, Mexico.
Email: daniel_mendoza@uaeh.edu.mx
Funding information
Consejo Nacional de Ciencia y Tecnología,
Grant/Award Number: A1-S-8892
K E Y W O R D S
catalysis, gold, hydroamination, hydrohydrazination, mesoionic carbenes
1 | INTRODUCTION
azides (CuAAC)[6] and the subsequent N-alkylation,
which readily delivers the desired 1,2,3-triazolylidene
With the pivotal discovery in 2001 by Gründemann and
coworkers,[1] the field of mesoionic carbenes (MICs)
has experienced a fast development.[2] These types of
ligands where the carbene center is not flanked by
heteroatoms in both sides of their structures have
attracted a great deal of attention as they have demon-
strated enhanced σ-donor properties as compared
with classical N-heterocyclic carbenes (NHCs).[3] The
mesoionic nature of these ligands arises from the fact
that their structures can only be represented as
zwitterions and not in the canonical neutral form.[4]
Among the several types of MICs available in the litera-
ture, 1,2,3-triazolylidenes have found a wide range of
applications as ligands for transition metals, typically
employed in a variety of catalytic organic transforma-
tions.[5] The success of the triazolylidene coordination
chemistry is related to the facile preparation of the
triazole precursors by means of the regioselective
copper(I)-catalyzed “click” cycloaddition of alkynes and
precursors. Owing to the ease in structural modification
in the triazolylidene scaffolds, great topological diversity
is achieved by changing the substituent appended at
the N1-, N3-, and C4-positions of the central triazole
core. This structural diversity significantly affects the
electronic and steric properties of the MICs, which in
turn accounts for the variation in the stability and reac-
tivity of the resulting complexes.
In the last decade, the exploration of novel structural
motifs has enabled the development of a variety of appli-
cations for NHCs. In particular, ring-fused NHC architec-
tures are highly desirable as it has been demonstrated
that the rotational lability of the carbene can greatly
influence the behavior and dynamics of the NHC-bound
metal complex.[7] Indeed, ring-fused NHCs have found
application as organocatalysts and ligands for stabiliza-
tion of low-valent species, and when containing axial
chirality, their metal complexes are exceptional catalysts
for a variety of asymmetric transformations.[8]
Appl Organomet Chem. 2020;e6098.
wileyonlinelibrary.com/journal/aoc
© 2020 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.6098

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CAMPOS-DOMINGUEZ ET AL.
Interestingly, despite the easy access to 1,2,3-triazole
produces in good yields the desired triazolium salts 1a–c
as crystalline colorless solids after purification by recrys-
tallization from acetonitrile–diethyl ether mixtures.
The identity of the triazolium salts 1a–c was conve-
niently assessed by 1H and 13C NMR spectroscopy
(Figures S1–S6) and elemental analysis. The formation of
the triazolium salts 1a–c was easily monitored by the
ligand platforms with various levels of substitution
and modification, only few examples of bicyclic
1,2,3-triazolium salts have been reported in the literature,
and their use is limited to ionic liquid applications.[9] To
the best of our knowledge, the preparation of multicyclic-
based 1,2,3-triazolylidene–metal complexes is yet to be
discovered.
1
appearance of a new signal in the H NMR spectrum in
With this background and in line with our research
devoted to metal triazolylidenes, we present herein the
synthetic strategy for the preparation of the first examples
of ring-fused benzoxazine-derived triazolium salts (1a–c)
and their respective gold(I)-1,2,3-triazolylidene complexes
2a–c. The full characterization of the triazolium salts
(1a–c) and the application of the triazolylidene gold com-
plexes (2a–c) as precatalysts in the hydroamination and
hydrohydrazination of terminal alkynes will be discussed.
the range of δ = 4.44–4.68 ppm, indicating methylation
of the triazolyl moiety (at N-3). In addition, the presence
of the characteristic singlet in H NMR due to the now
acidic triazolium protons in the region of δ = 8.87–9.90,
and the peaks at δ = 133.2–136.9 in 13C NMR belonging
to the C-5 atom, confirms the structure of the expected
cationic rings. The representative multiplets in the
aromatic area (7.13–8.06 ppm) belonging to the aryl frag-
ments are also consistent with the successful construction
of the ring-fused triazoliums.
1
Unambiguous characterization of the triazolium salts
1a and 1b was also achieved by X-ray diffraction study
with the molecular structures depicted in Figure 1.
Triazoliums 1a and 1b crystallized in the monoclinic
P21/m and triclinic P1 space groups, respectively. The
asymmetric unit in both structures contains a single
triazolium iodide unit with C–C and C–N bond distances
and C–C–N angles similar to other cationic analogues.[1,2]
2 | RESULTS AND DISCUSSION
The ring-fused benzoxazine-derived 1,2,3-triazoliums
1a–c were synthesized according to Scheme 1. Initially,
the aminophenol derivative was converted into the
organic azide using sodium nitrite under acidic condi-
tions, followed by the addition of sodium azide. The
alkylation of the hydroxyl group was carried out through
a deprotonation step using K2CO3 in the presence of
propargyl bromide. Interestingly, after workup, the
presence of the propargylated intermediate B was not
observed by thin-layer chromatography (TLC). Instead,
and likely favored by the refluxing reaction conditions
and the proximity of the alkyne and azide groups, the
intramolecular [2 + 3] cycloaddition took place, provid-
ing the respective 1,2,3-triazoles (I–III). This one-step
annulation process is notable as it does not require metal-
lic catalyst or rough reaction conditions (as previously
reported in the literature) to proceed.[10] The final
triazole N-alkylation step using excess of methyl iodide
]
In both crystal structures, the triazole and phenyl rings
are almost coplanar with maximum N2, N1, C13, and
C12 torsion angles of 12.6ꢀ. As expected, owing to the
presence of the methylene and ether moieties, the central
six-membered rings in 1a and 1b display a marked
deviation from coplanarity with respect to the triazole
and phenyl rings presenting C5, C6, C7, and C8 torsion
angles in the range of 35.9–45.5ꢀ.
To explore the coordination capabilities of the new
monotriazolium salts 1a–c, we tested their reactivity
with hexamethyldisilazane (KHMDS) in the presence of
AuCl (SMe2) under strict light absence (Scheme 2).
After workup and purification, the respective gold
SCHEME 1 Synthesis of ring-fused
triazoliums 1a–c

CAMPOS-DOMINGUEZ ET AL.
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FIGURE 1 Molecular structure of triazolium 1a (left) and 1b (right). Ellipsoids are shown at 50% of probability. Selected angles (ꢀ):
(1a) N3-C4-C5 106.0(10), (1b) N3-C4-C5 105.4(3)
SCHEME 2 Synthesis of gold(I)
complexes 2a–c
triazolylidenes 2a–c were obtained as crystalline powders
in good yields (82–92%). Complexes 2b and 2c are highly
soluble in a series of chlorinated solvents, toluene, tetra-
hydrofuran (THF), and acetonitrile, whereas complex 2a
displays only low solubility in DMSO.
The successful metalation of the triazolium salts was
clearly indicated by the disappearance of the low-field
triazolium proton resonance (located around 9 ppm) in
1H NMR spectroscopy and a slight upfield shift of the
N–CH3 group (Figures S7–S12). The new carbene-gold
peak appears in the range of 164–168 ppm in 13C NMR,
consistent with previously reported triazolylidene gold
complexes.[11]
Despite our numerous efforts to crystallize monome-
tallic complexes 2a–c, we were unsuccessful in obtaining
X-ray quality samples. Thus, in order to get more insight
into the structural features of the new gold complexes,
we carried out density functional theory (DFT) calcula-
tions, at the B3LYP/6-31G(d,p)/LANL2DZ level of theory
with Grimme et al.'s D3 correction[12] and using the
LANL2DZ pseudopotentials[13] only for transition metal
atoms. As illustrated in Figure 2, the gold centers in all
FIGURE 2 Optimized
density functional theory (DFT)
geometries of complexes 2a
(left), 2b (center), and 2c (right)

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CAMPOS-DOMINGUEZ ET AL.
complexes are close to the expected linear geometries,
which are common for Au(X) fragments coordinated to a
single carbene. The calculated bond distances for the
Au–MIC (2.027 Å, avg.) and Au–I (2.672 Å, avg.) moieties
also fall in the normal parameters for monodentate MIC
gold complexes reported in the literature.[11]
Recent studies have demonstrated unquestionably
that gold is an excellent Lewis acid for the selective
activation of unsaturated carbon–carbon bonds under
mild conditions.[14] In particular, NHC-based gold(I)
complexes have shown applicability as precatalysts in
various processes such as C–H bond functionalizations,
cyclization of enynes, and hydroaminations, among
others.[15]
With complexes 2a–c in hand, we decided to investi-
gate their catalytic performance in two important C–N
bond-forming processes. The first one involved the
hydrohydrazination of terminal alkynes employing
hydrazine as a nitrogen source, and the second refers to
the hydroamination of phenylacetylene, a process for
which several AuI-based catalysts have shown good
activity.[16] As an initial screening test for the
hydrohydrazination process, we carried out the stoichio-
metric reaction of hydrazine with phenylacetylene (80ꢀC
in toluene), a catalyst loading of 3 mol% and employing
AgSbF6 as halogen scavenger (to render the AuI active
species). As observed in Table 1, the MIC-based AuI com-
plexes 2b and 2c provide similar conversions under these
catalytic conditions with complex 2a being the less active
of the series (Entries 1–3). In order to challenge the
performance of the gold precatalysts, several reaction
conditions were modified, including the catalyst loading
and reaction temperatures. It can be observed that the
gradual decrease of the catalyst loading until 0.5 mol%
does not affect the conversion percentages for complexes
2b and 2c; however, complex 2a significantly decreases
its catalytic performance (70% conversion). Interestingly,
temperature can be decreased to 60ꢀC without loss on the
catalytic efficiency for complexes 2b and 2c (Entries
11 and 12).
optimized conditions of Table 2 but using half equivalent
of hydrazine results in the successful preparation of the
corresponding azines in good yields (90–94%) after simple
purification by means of a column chromatography
(Table 3, Figures S25–S30).
To further explore their catalytic performance,
complexes 2a–c were tested in the hydroamination of
phenylacetylene with aniline. The reactions were carried
out initially in CD3CN at 70ꢀC, with catalyst and AgSbF6
loadings of 5 mol%. The catalytic results were monitored
1
by H NMR spectroscopy over 6 h (Table 4). Interest-
ingly, complexes 2a–c exclusively produced compound
3, which is the result of a Markovnikov addition to
aniline with subsequent tautomerization of the enamine.
This result suggests that the rigidity provided by the
fused-ring architecture in the triazolylidene ligands
benefits the selectivity in this process. According to
Table 3 and as observed in the hydrohydrazination
process, complexes 2b and 2c display slightly better
catalytic conversions under the initial reaction condi-
tions (Entries 1–3).
Further evaluation on the optimized catalytic param-
eters demonstrates that the catalyst loading for 2b and 2c
can be decreased 10-fold (0.5 mol%) without significant
loss of the conversions (Entries 11 and 12). Likewise, as
in the hydrohydrazination reaction, the decrease in the
loading of complex 2a (0.1 mol%) gradually diminishes
the conversion down to 77% (Entry 13).
Considering the good conversions of complexes 2b
and 2c under low catalyst loadings, we decided to explore
the effect of the aniline electronics and sterics on the
catalytic performance. Table 5 reviews the most relevant
results. Complexes 2b and 2c both provided conversions
higher than 90% independent of the presence of electron-
donating or electron-withdrawing substituents in the
aniline substrate (Figures S31–S38). Additionally, the ste-
ric hindrance does not affect the catalytic performance as
the bulky anilines bearing the 2,4,6-trimethyl and
diisopropylphenyl groups were successfully converted
into products in good yields (Entries 13–16).
With the optimized conditions in hand, we next
tested complexes 2b and 2c in the hydrohydrazination of
several terminal alkynes with hydrazine. According to
Table 2, the corresponding hydrazones were obtained in
good to excellent yields, with catalyst 2b showing slightly
better results (Figures S13–S24).
Interestingly, during the optimization process, we
observed that the use of excess of hydrazine (1.5 equiv.)
resulted in the formation of a new product in low yield.
After careful analysis of the reaction mixture, we could
identify the new product as the result of a bis-
hydrohydrazination process. Thus, in order to favor the
production of the azines, we found that employing the
In order to rule out the formation of colloidal gold
particles as the active catalyst, the hydroamination of
phenylacetylene with aniline using complex 2b as
catalyst was disturbed by the addition of elemental
mercury at different reaction times (t = 0, 15, 30, and
60 min).[17] As shown in Figure 3, regardless of the
mercury addition time, the conversions are not affected
significantly. For instance, addition of mercury at t = 0
and 30 min decreases the conversions in only 6% and
4%, respectively. The small change in conversions
strongly suggests that even at 70ꢀC, the catalytic
conversions of complex 2b are performed essentially by
molecular species.

CAMPOS-DOMINGUEZ ET AL.
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TABLE 1 Optimization of the hydrohydrazination of phenylacetylene
Entry
[Cat]
2a
2b
2c
[Cat] (mol%)
Temp (ꢀC)
Yield (%)a
1
3
80
80
80
80
80
80
80
80
70
70
60
60
25
25
88
99
99
70
99
99
99
98
98
96
97
95
84
80
2
3
3
3
4
2a
2b
2c
1
5
1
6
1
7
2b
2c
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
8
9
2b
2c
10
11
12
13
14
2b
2c
2b
2c
Note: Reaction conditions: phenylacetylene (1.0 mmol), hydrazine (1.2 mmol), and toluene (3 ml).
aIsolated yields as the average of two runs.
TABLE 2 Scope of the hydrohydrazination of terminal alkynes with hydrazine
Entry
[Cat]
2b
2c
R
Yield (%)a
1
Ph
99
97
91
91
92
84
89
83
99
94
96
94
2
Ph
3
2b
2c
4-(OMe)Ph
4-(OMe)Ph
4-(Br)Ph
4-(Br)Ph
2-(NH2)Ph
2-(NH2)Ph
2-(Me)Ph
2-(Me)Ph
3-Pyridyl
3-Pyridyl
4
5
2b
2c
6
7
2b
2c
8
9
2b
2c
10
11
12
2b
2c
Note: Reaction conditions: alkyne (1.0 mmol), hydrazine (1.2 mmol), and toluene (3 ml).
aIsolated yields as the average of two runs.

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CAMPOS-DOMINGUEZ ET AL.
TABLE 3 Bis-(hydrohydrazination) of terminal alkynes with hydrazine
Note: Reaction conditions: alkyne (0.5 mmol), hydrazine (1.2 mmol), and toluene (3 ml). Isolated yields as the average of two runs.
TABLE 4 Optimization of the hydroamination of phenylacetylene with aniline
Entry
[Cat]
2a
2b
2c
[Cat] (mol%)
Yield (%)a
1
5
92
99
98
86
99
96
84
98
94
81
98
92
77
91
88
2
5
3
5
4
2a
2b
2c
3
5
3
6
3
7
2a
2b
2c
1
8
1
9
1
10
11
12
13
14
15
2a
2b
2c
0.5
0.5
0.5
0.1
0.1
0.1
2a
2b
2c
Note: Reaction conditions: phenylacetylene (0.5 mmol), aniline (0.55 mmol), and CD3CN (1 ml).
aIsolated yields as the average of two runs.
In general, the catalytic hydrohydrazination perfor-
mances of complex 2b compares well with mesoionic
[MIC–Au]+ catalysts reported by Manzano et al.,[16c]
Tolentino et al.,[16b] and our group[11h,k] in terms
of catalyst loading, conversions, time, and reaction
temperatures. However, its performance is still behind

CAMPOS-DOMINGUEZ ET AL.
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TABLE 5 Scope of the hydroamination of phenylacetylene with substituted anilines
Entry
1
[Cat]
2b
2c
Ar
Yield (%)a
Ph
95
92
97
98
95
91
90
86
89
91
93
89
87
90
86
88
2
Ph
3
2b
2c
2-(Me)Ph
2-(Me)Ph
4-(Me)Ph
4-(Me)Ph
4-(OMe)Ph
4-(OMe)Ph
4-(NO2)Ph
4-(NO2)Ph
2,6-(Me2)Ph
2,6-(Me2)Ph
2,4,6-(Me3)Ph
2,4,6-(Me3)Ph
2,6-(iPr)2Ph
2,6-(iPr)2Ph
4
5
2b
2c
6
7
2b
2c
8
9
2b
2c
10
11
12
13
14
15
16
2b
2c
2b
2c
2b
2c
Note: Reaction conditions: phenylacetylene (0.5 mmol), substituted aniline (0.55 mmol), and CD3CN (1 ml).
aIsolated yields as the average of two runs.
FIGURE 3 Mercury poisoning tests
at different reaction times for the
hydroamination of phenylacetylene with
aniline catalyzed by complex 2b.
Reaction conditions: phenylacetylene
(0.5 mmol), aniline (0.55 mmol), catalyst
(0.5 mol%,), AgSbF6 (0.5 mol%)
the
[
iPrBiCAACAu]+ complex recently reported by
known Michelet L-shaped [NHC–Au]+ complex,[8a] it
performs similarly than the other catalysts presented
in Table 6.
Yazdani et al.[18] In terms of the hydroamination,
even though complex 2b is not as active as the

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CAMPOS-DOMINGUEZ ET AL.
TABLE 6 Comparison of complex 2b with recently reported NHC–Au-based hydrohydrazination and hydroamination catalysts
Substrate
(mmol)
Conversion
(%)
Catalyst
mol% Additive
Alkyne (mmol)
Temp (ꢀC) Time (h)
100 12
1.0a
KB(C6F5)4
(1.0)
H4N2 (0.32)
84
5.0b
KB(C6F5)4
(1.0)
H4N2•H2O
90
20
4
(0.50)
3.0c
KB(C6F5)4
(3.0)
H4N2 (1.20)
97
99
80
20
12
0.5d
KB(C6F5)4
(0.5)
H4N2 (0.357)
2
2b
0.5e
0.5f
AgSbF6 (0.5)
AgBF4 (1.0)
H4N2 (1.20)
99
99
60
70
12
6
PhNH2 (0.55)
0.01g
NaB(C6F5)4
(0.16)
PhNH2 (0.55)
76
80
37
2b
0.5e
AgSbF6 (0.5)
PhNH2 (0.55)
95
70
6
aTolentino et al.[16b]
bManzano et al.[16c]
cMendoza-Espinosa et al.[11h]
dYazdani et al.[18]
eThis work.
fFlores-Jarillo et al.[11k]
gTang et al.[8a]

CAMPOS-DOMINGUEZ ET AL.
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SCHEME 3 Proposed general reaction mechanism for the hydroamination and hydrohydrazination processes catalyzed for 2a–c
Based on previous reports,[19] a plausible general
reaction mechanism for the MIC–Au(I)-catalyzed
hydroamination and hydrohydrazination processes is
depicted in Scheme 3. The initial step involves the gener-
ation of a gold(I)-activated alkyne complex (A) obtained
from the reaction of the proper MIC–Au(I) complex with
AgSbF6 and phenylacetylene. The amine/hydrazine
reagent coordinates to the electron-deficient intermedi-
ate A, forming complex B, which then undergoes a
nucleophilic attack by the nitrogen of the amine/
hydrazine resulting in the formation C. Intermediate
C experiments a proton transfer to form a gold(I)-alkene
species D, which in the presence of phenylacetylene
releases the active catalyst A and the enamine E.
Finally, after a tautomerization process, the final product
F is obtained.
3 | CONCLUSIONS
In summary, a series of ring-fused benzoxazine-derived
triazolium salts (1a–c) have been synthesized stepwise
via intramolecular alkyne–azide cycloaddition and
N-alkylation procedures using ortho-aminophenols as
starting materials. Their one-pot deprotonation with
KHMDS in the presence of AuCl (SMe2) allowed for the
preparation of the corresponding triazolylidene gold(I)
complexes (2a–c) in high yields. The new triazolylidene
gold complexes were tested as precatalysts in the
hydroamination and hydrohydrazination of terminal
alkynes employing aniline derivatives and hydrazine as
the nitrogen sources, respectively. In both processes,
complexes 2b and 2c, which feature electron-
withdrawing (Cl) and electron-donating groups (Me),

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CAMPOS-DOMINGUEZ ET AL.
respectively, are the best catalysts of the series. These
results indicate that the electronic substitution in the
aromatic ring of the triazolylidene ligands in 2b and 2c is
not relevant for catalytic purposes and that their
enhanced performance is likely related to their higher
solubility under the catalytic conditions. Mercury
poisoning tests evaluated in the hydroamination of
phenylacetylene indicate that even at 70ꢀC, the catalytic
conversions are performed by homogeneous molecular
species, highlighting the robustness of the new gold
complexes. Further exploration on the catalytic potential
of complexes 2a–c in C–N bond-forming processes is a
currently research topic in our laboratory.
geometries were confirmed as local minima performing
normal mode frequency analyses at the same level of
theory.
4.2.1 | General procedure for the
synthesis of triazoles I–III
In a 50-ml round-bottomed flask equipped with a mag-
netic stirring bar was placed 1 equiv. of azide in 20 ml of
acetone as solvent, followed by the addition of 3 equiv. of
propargyl bromide and 1 equiv. of potassium carbonate.
The resulting solution was refluxed for 24 h, followed by
extraction with EtOAc (3 × 25 ml). The collected organic
layers were dried with MgSO4, and the solvent was
removed under vacuum to give the corresponding
triazole. After removal of ethyl acetate, the crude residue
was purified by column chromatography (EtOAc/hexane)
to afford pure triazoles.
4 | EXPERIMENTAL SECTION
4.1 | General considerations
Commercially available reagents and solvents were used
as received. All manipulations related to the synthesis of
gold complexes were performed under an atmosphere of
dry nitrogen using standard Schlenk techniques. Solvents
were dried by standard methods and distilled under
nitrogen. Melting points were determined on a Fisher-
Johns apparatus and are uncorrected. NMR spectra were
obtained with a Bruker Ascend (400 MHz) spectrometer.
Elemental analyses were obtained with a Thermo Fin-
negan CHNSO-1112 apparatus and a Perkin Elmer Series
II CHNS/O 2400 instruments. X-ray diffraction analyses
were collected in an Agilent Gemini diffractometer using
Mo Kα radiation (l = 0.71073 Å). Data were integrated,
scaled, sorted, and averaged using the CrysAlisPro soft-
ware package. The structures were solved using direct
methods and SHELX 2014 and refined by full matrix least
squares against F2.[20] All non-hydrogen atoms were
refined anisotropically. The position of the hydrogen
atoms was kept fixed with common isotropic display
parameters. The crystallographic data and some details of
the data collection and refinement are given in Table S1.
Triazole I
The general procedure was followed using 0.49 g
(5.62 mmol) of 2-azidophenol, 0.95 ml (10.89 mmol) of
propargyl bromide, and 0.51 g (5.62 mmol) of potassium
carbonate to give 0.54 g (87% yield) of I as beige solid.
1
mp = 59–61ꢀC. H NMR (CDCl3, 400 MHz) δ: 7.97 (dd,
J = 8 Hz, J = 1.6 Hz, 1H), 7.55 (s, 1H), 7.20 (td,
J = 8.4 Hz, J = 1.2 Hz, 1H), 7.10 (m, 2H), 5.31 (s, 2H). 13C
NMR (CDCl3, 100 MHz) δ: 145.1, 129.0, 128.9, 127.3,
123.9, 123.1, 117.8, 116.7, 61.8. High-resolution mass
spectrometry (HRMS) (electrospray ionization–time-of-
flight [ESI–TOF]) m/z calcd for C9H7N3O1 [M + H]+:
174.0661, found m/z 174.0663.
Triazole II
The general procedure was followed using 0.52 g
(3.09 mmol) of 2-azido-5-chlorophenol, 0.80 ml
(9.28 mmol) of propargyl bromide, and 0.43 g (3.09 mmol)
of potassium carbonate to give 0.57 g (91% yield) of II as
beige solid. mp = 144–146ꢀC. 1H NMR (CDCl3, 400 MHz)
δ: 7.97 (d, J = 9.6 Hz, 1H), 7.61 (s, 1H), 7.14 (m, 2H), 5.39
(s, 2H). 13C NMR (CDCl3, 100 MHz) δ: 145.7, 134.2,
129.1, 126.9, 123.3, 122.5, 118.2, 117.4, 62.1. HRMS
(ESI–TOF) m/z calcd for C9H6N3O1Cl1 [M + H]+:
208.0272, found m/z 208.0274.
4.2 | Computational details
Initial geometries were obtained by converting the
SMILES representation of the ligands to three-
dimensional coordinates and then coordinating it along
with the iodine atom to the metal center by hand. Local
geometry optimizations of the complexes were then
performed with the Gaussian 09 software with DFT at
the B3LYP/6-31G(d,p)/LANL2DZ level of theory with
Grimme et al.'s D3 correction[12] using the LANL2DZ
pseudopotentials[13] only for transition metal atoms. All
Triazole III
The general procedure was followed using 0.89 g
(5.96 mmol) of 2-azido-4-methylphenol, 1.54 ml
(17.9 mmol) of propargyl bromide, and 0.91 g (5.96 mmol)
of potassium carbonate to give 0.91 g (90% yield) of III as
brown solid. mp = 107–110ꢀC. 1H NMR (CDCl3,
400 MHz) δ: 7.82 (d, J = 1.6 Hz, 1H), 7.57 (s, 1H), 7.09

CAMPOS-DOMINGUEZ ET AL.
11 of 13
(dd, J = 8.4, J = 1.6 Hz 1H), 6.95 (d, J = 8.4, Hz H), 5.30
(s, 2H), 2.34 (s, 3H). 13C NMR (CDCl3, 100 MHz) δ:
142.8, 132.7, 129.3, 128.8, 127.4, 123.3, 117.3, 116.7, 61.6,
20.7. HRMS (ESI–TOF) m/z calcd for C10H9N3O1
[M + H]+: 188.0818, found m/z 118.0820.
12.34; calcd for C11H12IN3O C, 40.14; H, 3.68; N, 12.77.
HRMS (ESI–TOF) m/z calcd for C11H12N3O [1c–I]+:
202.0980, found m/z 202.0984.
4.2.2 | General procedure for the
synthesis of gold complexes 2a–c
General procedure for the synthesis of triazolium salts
1a–c
Methyl iodide (26 mmol) was added to a 10-ml acetoni-
trile solution of the proper triazole (1.74 mmol), and the
resulting suspension was refluxed for 24 h. After room
temperature was reached, the solvent was reduced to 2/3
of the original volume, and diethyl ether was added until
a precipitate was formed. The solid was collected by
filtration and washed thoroughly with cold diethyl ether.
Pure product was colorless crystals after recrystallization
with acetonitrile/diethyl ether (1:3).
In strict absence of light, choloro(dimethylsulfide)gold
(0.21
mmol),
potassium
hexamethyldisilazide
(0.24 mmol), and the proper triazolium salt (0.20 mmol)
were combined in a Schlenk flask and dissolved in THF
(7 ml) at −78ꢀC. The resulting mixture was stirred for
12 h. The final clear suspension was dried under vacuum,
and the residue was washed with hexane (3 ml) and
diethyl ether (3 ml) and further extracted with benzene.
After cannula filtration and removal of the solvent, the
crude product is dissolved in 1 ml of dichloromethane
(DCM) and precipitated by addition of 10 ml of petro-
leum ether. The solid is filtered and dried under vacuum,
yielding the title product as white solid.
Triazolium 1a
Yield 80% (1.39 mmol). mp = 182–184ꢀC. 1H NMR
(400 MHz, DMSO-d6) δ: 8.90 (s, 1H, CHtrz), 8.02
(d, J = 8.2 Hz, 1H, CHar), 7.60 (t, J = 7.9 Hz, 1H, CHar),
7.35 (d, J = 8.0 Hz, 2H, CHar), 5.71 (s, 2H, OCH2), 4.46 (s,
3H, NCH3). 13C NMR (101 MHz, DMSO-d6) δ: 147.6 (Cq),
133.2 (CHtz), 128.7 (CHar), 124.3 (CHar), 121.8 (Cq), 119.1
(CHar), 117.9 (CHar), 61.2 (OCH2), 41.1 (NCH3).
Found: C, 38.04; H, 3.18; N, 13.27; calcd for
C10H10IN3O C, 38.12; H, 3.20; N, 13.34. HRMS
(ESI–TOF) m/z calcd for C10H10N3O [1a–I]+: 188.0824,
found m/z 118.0822.
Complex 2a
Yield 90% (0.180 mmol). mp = 115–117ꢀC. 1H NMR
(400 MHz, DMSO-d6) δ: 7.96 (dd, J = 8.1, 1.4 Hz, 1H,
CHar), 7.52 (t, J = 7.9 Hz, 1H, CHar), 7.35–7.26 (m, 2H,
CHar), 5.69 (s, 2H, OCH2), 4.43 (s, 3H, NCH3). 13C NMR
(101 MHz, DMSO-d6) δ: 168.6 (Au-C), 147.8 (Cq), 138.0
(CHar), 132.3 (CHar), 128.8 (Cq), 123.9 (CHar), 118.9
(CHar), 117.9 (CHar), 62.3 (OCH2), 43.0 (NCH3).
Found: C, 23.12; H, 1.45; N, 8.55; calcd for
C10H9AuIN3O C, 23.50; H, 1.78; N, 8.22. HRMS
(ESI–TOF) m/z calcd for C20H18AuN2O6 [M − I + 1a]+:
571.1157, found m/z 571.1161.
Triazolium 1b
Yield 72% (1.25 mmol). mp = 198–200ꢀC. 1H NMR
(400 MHz, DMSO-d6) δ: 8.87 (s, 1H, CHtrz), 8.05 (d,
J = 8.7 Hz, 1H, CHar), 7.56 (d, J = 2.1 Hz, 1H, CHar),
7.41 (dd, J = 8.7, 2.2 Hz, 1H, CHar), 5.73 (s, 2H, OCH2),
4.44 (s, 3H, NCH3). 13C NMR (101 MHz, DMSO-d6) δ:
148.4 (Cq), 137.0 (Cq), 133.0 (CHtz), 128.8 (CHar), 124.3
(CHar), 120.9 (Cq), 119.3 (CHar), 118.6 (Cq), 61.6 (OCH2),
41.0 (NCH3). Found: C, 34.67; H, 2.29; N, 12.18; calcd for
C10H9ClIN3O C, 34.36; H, 2.60; N, 12.02. HRMS
(ESI–TOF) m/z calcd for C10H9ClN3O [1b–I]+: 222.0434,
found m/z 222.0438.
Complex 2b
Yield 92% (0.184 mmol). mp = 141–143ꢀC. 1H NMR
(400 MHz, DMSO-d6) δ: 7.95 (d, J = 8.7 Hz, 1H, CHar),
7.50–7.49 (m, 1H, CHar), 7.43–7.41 (m, 1H, CHar), 5.60
(s, 2H, OCH2), 4.29 (s, 3H, NCH3). 13C NMR (101 MHz,
DMSO-d6) δ: 164.4 (Au-C), 148.5 (Cq), 136.0 (Cq), 128.8
(CHar), 123.9 (CHar), 121.2 (Cq), 119.3 (CHar), 119.0
(Cq), 62.7 (OCH2), 42.7 (NCH3). Found: C, 21.88; H,
1.29; N, 7.41; calcd for C10H8AuClIN3O C, 22.02; H,
1.48; N, 7.70. HRMS (ESI–TOF) m/z calcd for
C20H16Cl2AuN2O6 [M − I + 1b]+: 639.0377, found m/z
639.0380.
Triazolium 1c
Yield 89% (1.55 mmol). mp = 177–179ꢀC. 1H NMR
(400 MHz, CDCl3) δ: 9.90 (s, 1H, CHtrz), 7.74 (s, Hz, 1H,
CHar), 7.33 (dd, J = 8.5, 2.0 Hz, 1H, CHar), 7.14 (d,
J = 8.5 Hz, 1H, CHar), 5.74 (s, 2H, OCH2), 4.68 (s, 3H,
NCH3), 2.44 (s, 3H, CH3). 13C NMR (101 MHz, CDCl3) δ:
145.3 (Cq), 134.4 (CHtz), 134.0 (CHar), 132.3 (Cq), 130.2
(Cq), 120.9 (Cq), 118.9 (CHar), 117.6 (CHar), 61.5 (OCH2),
42.07 (NCH3), 20.8 (CH3). Found: C, 39.91; H, 3.85; N,
Complex 2c
Yield 82% (0.166 mmol). mp = 133–135ꢀC. 1H NMR
(400 MHz, DMSO-d6) δ: 7.67 (bs, 1H, CHar), 7.27–7.25
(m, 1H, CHar), 7.11 (d, J = 8.5 Hz, 1H, CHar), 5.40 (s, 2H,
OCH2), 4.43 (s, 3H, NCH3), 2.43 (s, 3H, CH3). 13C NMR

12 of 13
CAMPOS-DOMINGUEZ ET AL.
(101 MHz, DMSO-d6) δ: 166.7 (Au-C), 145.4 (Cq), 135.6
(CHar), 133.7 (Cq), 132.7 (Cq), 128.3 (Cq), 118.7 (CHar),
117.4 (CHar), 62.0 (OCH2), 42.2 (NCH3), 20.9 (CH3).
Found: C, 25.50; H, 1.99; N, 8.17; calcd for
C11H11AuIN3O C, 25.16; H, 2.11; N, 8.00. HRMS
(ESI–TOF) m/z calcd for C22H22AuN2O6 [M − I + 1c]+:
599.1470, found m/z 599.1473.
AUTHOR CONTRIBUTIONS
Emmanuel Campos-Dominguez: Data curation;
formal analysis; investigation; methodology. Jose
M. Vasquez-Perez: Data curation; formal analysis;
methodology; validation. Susana Rojas-Lima: Formal
analysis; investigation; validation. Heraclio Lopez-Ruiz:
Conceptualization; formal analysis; methodology.
CONFLICT OF INTEREST
4.2.3 | Catalytic procedure for the
hydrohydrazination of alkynes using
complexes 2a–c
There are no conflicts of interest to declare.
DATA AVAILABILITY STATEMENT
The data that support the findings of this study are
available in the Supporting Information of this article.
Under nitrogen, the catalyst (0.5 mol%) and AgSbF6
(0.5 mol%) were charged in a 5-ml screw-capped vial
equipped with a magnetic bar; 3 ml of anhydrous toluene
was added, and the mixture was stirred for 5 min
followed by the addition of the alkyne (1.0 mmol) and
anhydrous hydrazine (1.2 mmol). The reaction mixture
was heated at 60ꢀC for 12 h. The reaction mixture was
filtered through Celite, and the supernatant concentrated
under vacuum. The products were purified directly by
column chromatography on silica gel using benzene/
hexane as eluent.
ORCID
Daniel Mendoza-Espinosa https://orcid.org/0000-0001-
9170-588X
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ACKNOWLEDGMENT
We are grateful to the Consejo Nacional de Ciencia y
Tecnología (Project A1-S-8892) for the financial support.

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SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.
How to cite this article: Campos-Dominguez E,
Vasquez-Perez J, Rojas-Lima S, Lopez-Ruiz H,
Mendoza-Espinosa D. Gold(I) complexes bearing
ring-fused benzoxazine-derived triazolylidenes and
their use in C–N bond-forming processes. Appl
Organomet Chem. 2020;e6098. https://doi.org/10.
1002/aoc.6098
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