Catalytic Activity of Gold(I) Complexes with Hemilabile P,N Ligands

Article abstract of DOI:10.1002/cplu.201600562

Two new cationic dinuclear gold(I) complexes, [Au₂{μ(P,N)-5}₂]X₂—in which X=NTf₂ (7; Tf=trifluoromethanesulfonate) or SbF₆ (8) and 2-(diphenylphosphanyl)benzonitrile (5) is a P,N-bridging donor—have been synthesized and structurally characterized. These air-stable species and their dimeric and polymeric analogues possessing 1′-(diphenylphosphanyl)-1-cyanoferrocene (1) as the bridging ligand, [Au₂{μ(P,N)-1}₂](NTf₂)₂ and [Au{μ(P,N)-1}]_n[SbF₆]_n, were used as precatalysts in various Au-mediated C?C and C?O bond-forming reactions. The reactivity of these complexes revealed the hemilabile nature of their P,N ligands. In the series of tested precatalysts, complex 8 exerted particularly high catalytic activity at low Au loading, even in reactions that usually require high amounts of gold catalyst to proceed efficiently under standard reaction conditions.

Full text of DOI:10.1002/cplu.201600562

Accepted Article
Title: Catalytic Activity of Au(I) Complexes with Hemilabile P,N-Ligands
Authors: Bastien Michelet, David Leboeuf, Christophe Bour, Karel
Skoch, Filip Horky, Petr Stepnicka, and Vincent Gandon
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Catalytic Activity of Au(I) Complexes with Hemilabile P,N-Ligands
Bastien Michelet,[a] David Lebœuf,[a] Christophe Bour,[a] Karel Škoch,[b] Filip Horký,[b] Petr Štěpnička*[b]
and Vincent Gandon*[a]
Abstract: Two new cationic dinuclear gold(I) complexes, [Au2(µ(P,N)-
5)2]X2, where
X
=
NTf2 (7) or SbF6 (8), containing 2-
(diphenylphosphanyl)benzonitrile (5) as a P,N-bridging donor have
been synthesized and structurally characterized. These air-stable
species and their dimeric and polymeric analogues possessing 1’-
(diphenylphosphanyl)-1-cyanoferrocene (1) as the bridging ligand,
[Au2(µ(P,N)-1)2](NTf2)2 (3) and [Au(µ(P,N)-1)]n[SbF6]n, were used as
pre-catalysts in various Au-mediated C–C and C–O bond forming
reactions. The reactivity of these complexed revealed hemilabile
nature of their P,N-ligands. In the series of tested pre-catalysts,
complex 8 exerted particularly high catalytic activity at low Au loading,
even in reactions that usually require high amounts of gold catalyst to
proceed efficiently under standard reaction conditions.
Scheme 1. Typical synthesis Au(I) pre-catalysts by chloride abstraction.
In spite of the generally high stability of gold(I) pre-catalysts,
decomposition may occur during prolonged storage or under
reaction conditions.[6] The rapid decay of the active species can
be blamed for low turnover numbers, which remain an issue in
gold catalysis.[ 7 ] Typically, quite high catalyst loadings are
required (> 1 mol%), although some large ligands or counterions
and silver-free promoters have allowed to circumvent this problem
in particular cases.[8]
Introduction
Organogold(I) complexes have become very popular in synthetic
organic chemistry due to their ability to catalyze a myriad of useful
transformations. The success of this research area is linked with
its close combination with coordination and organometallic
chemistry, which aided in finding efficient catalysts and
appropriate reaction conditions.[ 1 , 2 , 3 ] The majority of Au(I)
complexes used now as pre-catalysts combine one strongly
coordinating monodentate ligand L (phosphines, N-heterocyclic
carbenes, etc.) with a weakly coordinating one (typically nitriles
A stabilization of reactive intermediates can be achieved through
the use of hemilabile ligands that combine strongly and weakly
coordinating groups in their molecules.[ 9 ] The weaker bond
between the weakly binding donor moiety and the metal ion can
be cleaved by the substrate and formed again once the catalytic
product is released from the coordination sphere. Due to chelate
effect, the complexes derived from hemilabile ligands are typically
more stable than simple solvent adducts. In contrast to other
noble metal-based catalysts, the synthesis of Au(I) compounds
containing hemilabile ligands (mostly P,N- or carbene,N-donors)
has not attracted considerable attention.[10] In fact, the preferred
linear geometry of [LAuX] complexes[2h,2i] makes the chelate
formation unlikely. On the other hand, the bis(monodentate)
coordination mode allowed by hemilabile bifunctional ligands can
give rise to Au(I) dimers (Figure 1, A) or higher aggregates.[11]
These assemblies can be stabilized by aurophilic interactions.[12]
–
and anions such as NTf2 and OTf–).[ 4 ] They are usually
synthesized by chloride abstraction from the respective [LAuCl]
with a silver(I) salt of a weakly coordinating anion (AgX, Scheme
1). The removal of the chloride can be either achieved in situ or
used to synthesize well-defined catalytically active complexes
such as [LAu][NTf2], [LAu][OTf], or the corresponding nitrile
adducts [LAu(RCN)]X.[5]
[a]
[b]
Dr. B. Michelet, Dr. D. Lebœuf, Dr. C. Bour, Prof. V. Gandon
Institut de Chimie Moléculaire et des Matériaux d’Orsay, CNRS
UMR 8182, Univ. Paris-Sud, Université Paris-Saclay, bâtiment 420,
91405 Orsay cedex (France)
E-mail: vincent.gandon@u-psud.fr
Dr. K. Škoch, F. Horký, Prof. Dr. P. Štěpnička
Department of Inorganic Chemistry
Faculty of Science, Charles University
Hlavova 2030, 12840 Prague (Czech Republic)
E-mail: petr.stepnicka@natur.cuni.cz
Supporting information for this article is given via a link at the end of
the document.
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Figure 1. Examples of Au(I) dimers [L = strongly coordinating ligand group
(phosphine, NHC, etc.), Z = weakly coordinating moiety (nitrile, amine, etc.),
Mes = mesity, BArF = tetrakis{3,5-bis(trifluoromethyl)phenyl}borate].
Scheme 2. Synthesis and mutual conversion of Au(I) complexes with
phosphanylnitrile 1 (tht = tetrahydrothiophene).
Applications of such compounds in catalysis have been only
rarely mentioned. For instance, Limbach and coworkers reported
that the (NHC,N)Au(I) dimers B and C are exceptionally active in
cycloisomerization of an -alkynylfuran, referred to as
“problematic” under classical conditions, at Au loading of 0.13
mol%.[10h] Since both gold atoms in these pre-catalysts are
coordinatively saturated, it seems clear that the compounds easily
split into active monomers under the reaction conditions by
dissociation of the Au-N bonds. However, such a dissociation can
be difficult, as reported by Zhang et al. for complex D, which
proved to be less active than the corresponding monomeric
precursor generated in situ.[10k] Hashmi and coworkers also
described the deactivation of Au(I) derivatives of P,N-ligands
through the formation of aggregates.[13] We have recently used 1’-
(diphenylphosphanyl)-1-cyanoferrocene (1) as a hybrid P,N-
ligand to synthesize various Au(I) complexes (Scheme 2).[10l]
Treatment of the phosphane complex [AuCl(1-κP)] (2) with
AgNTf2 led to the symmetrical dimer [Au(µ(P,N)-1)]2(NTf2)2 (3) in
which the phosphanylnitrile connects two gold centers as a P,N-
bridge (no Au-Au bond was detected). On the other hand, an
analogous reaction of 2 with Ag[SbF6] gave rise to coordination
polymer [Au(µ(P,N)-1)]n[SbF6]n (4). The hemilabile coordination of
ligand 1 was confirmed by the reaction with Bu4NCl which
transformed 3 and 4 back into 2.
Complexes 3 and 4 are easy-to-handle and air-stable solids,
showing no sign of decomposition after weeks when stored in the
dark. As pre-catalysts, they were used in low loading for Au(I)-
mediated cyclizations of 2-en-4-yn-1-ols into furans (0.01 mol%
Au loading for 3, 0.1 mol% for 4).[10l] The synthesis of 1,3-oxazoles
by Au(I)-catalyzed oxidative cyclization of terminal alkynes with
nitriles was also successfully carried out using 3 and 4 (5 mol%
Au loading).[10l] In each case, no silver salts were added to
activate the complexes, which is appreciable if one considers the
negative role that silver can play in gold catalysis.[5b,14] As an
extension of our recent work, we describe herein the synthesis of
new
Au(I)
dimers
comprising
2-
(diphenylphosphanyl)benzonitrile[15] as a P,N-ligand and further
explore applications of such species in gold catalysis.
Results and Discussion
Au(I) complexes with 2-(diphenylphosphanyl)benzonitrile
2-(Diphenylphosphanyl)benzonitrile (5) reacts with [AuCl(tht)] in
the expected manner under the replacement of the weakly
coordinating tetrahydrothiophene (tht) ligand to afford phosphine
complex 6 (Scheme 2). Subsequent chloride removal with silver(I)
salts result in the formation of dinuclear complexes 7 and 8 in
which the phosphanylnitrile donor takes up the vacant
coordination site and coordinates as a P,N-bridging donor.
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with the parameters reported for 3[10l] while being slightly longer
than those found in the structure of [AuCl(PPh3)] (Au-P 2.228(1)
Å)[ 22 ] and [Au(PPh3)(MeCN)][SbF6] (Au-P 2.228(1) Å, Au-N
2.038(5) Å).[23] As evidenced by the torsion angle C7-C1-C2-P of
15.2(7)°, the 1,2-disubstituted benzene ring is somewhat twisted,
presumably due to the steric demands of the proximal functional
groups. The intramolecular Au···Au distance of ca. 3.7 Å rules out
24
]
any in-dimer aurophilic interaction[
and no significant
intermolecular Au···Au contacts were detected in the structure
either.
Scheme 3. Preparation of Au(I) complexes with 2-(diphenylphosphanyl)-
benzonitrile (tht = tetrahydrothiophene).
Complexes 6-8 are isolated as colorless solids that are stable to
air but should be stored in the dark to prevent decomposition.
Their 1H NMR spectra are little informative, only showing
complicated multiplets due to the aromatic protons. The 31P NMR
spectra of 6-8 contain singlet resonances, whose chemical shifts
increase in the order 8 < 7 < 6. The coordination of the nitrile
moiety is manifested through a shift of the CN band in the IR
spectra, which is observed at 2225 cm–1 for 6 and at 2281 cm–1
for both 7 and 8. The shift of these bands to higher energies upon
coordination of the nitrile moiety, observed also in the case of
Au(I)-1 complexes,[10l] points to a low contribution of π-back
bonding to the CN  Au interaction.[16] Notably the CN band of
the representative dimeric complex 8 shifts to higher energies
upon dissolution in dichloromethane (compare 2281 with a
shoulder at 2267 cm−1 in the solid state with 2306 cm−1 in the
solution), suggesting that the nitrile group remains coordinated in
the solution.
Structure determination carried out for 8 revealed that the
compound is a symmetrical dimer in which two phosphanylnitrile
ligands coordinate as P,N-bridges between equivalent gold
centers. According to a search in the Cambridge Structural
Database,[ 17 ] structurally characterized compounds featuring
neutral P,N-donors as bridges between two Au(I) centers are not
unprecedented. However, apart for the aforementioned
complexes containing 1’-(diphenylphosphanyl)-1-cyanoferrocene
as a ligand, they are limited to compounds resulting from various
phosphanylated heterocycles and Schiff bases. Thus, in addition
to compound D (Figure 1), they are represented by the dimers
[Au2(µ-L)2]X2, where L = 2-(dimethylphosphanyl)pyridine, [10a] 2-
(diphenylphosphanyl)-N-(isopropylidene)aniline,[10b] 2-(diphenyl-
Figure 2. PLATON[25] plot of the complex cation in the structure of 8 with
displacement ellipsoids scaled to the 30% probability level. Prime-labeled atoms
are generated by crystallographic inversion. Selected distances and angles (in
Å and deg): Au-P 2.242(1), Au-N’ 2.051(5), Au···Au’ 3.7209(6), P-Au-N’
173.1(1), C1-C7-N 177.9(6), C7-N-Au’ 156.1(5).
Catalytic evaluation
Complexes 3, 4, 7 and 8 were tested as pre-catalysts in various
C–C and C–O bond forming reactions. The first of the tested
reactions, an intramolecular hydroalkylation of ene--ketoamide 9
(Table 1), is typically referred to as a problematic one. Indeed, it
requires a prolonged heating in refluxing toluene, which promotes
decomposition of the active gold species. Hence, high Au
loadings (10 mol%) are required with classical pre-catalyst such
as [(Ph3P)AuCl]/AgSbF6 (entries 1 and 2) as well as with
preformed cationic complexes.[8d,g,h,26]
Table 1. Au(I)-Catalyzed Hydroalkylation of Ene--Ketoamide 9.[a]
phosphanyl)-1-methylimidazole,[10c]
tris(2-isopropyl-1H-
18
]
imidazolyl)phosphane,[
diazafluorene,[
9-(2-(diphenylphosphanyl)ethyl)-4,5-
19
]
diphenyl(2-imino-3,3-
dimethylbutyl)phosphane[ 20 ] and 1’-(diphenylphosphanyl)-1-(2-
pyridyl)ferrocene[21] (X is usually a simple anion).
Entry
[Au]
x
Conv [%][b]
The equivalent Au(I) ions in 8 are nearly linearly coordinated (P-
Au-N  173°) and the Au-P and Au-N bond lengths compare well
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1
2
3
4
5
6
7
[(Ph3P)AuCl]/AgSbF6
1[c]
0
[a] c = 0.2 M. [b] Conversion was determined by 1H-NMR analysis of the
crude product. The yield of the isolated product is given in parentheses. [c]
1 h.
[(Ph3P)AuCl]/AgSbF6
10[c]
0.5
1
100 (85)
3
4
7
8
8
77
On the other hand, the cycloisomerization of enyne 13, chosen for
a further catalytic evaluation (Table 3), is known to proceed at
room temperature, but gives rise to a mixture of isomers, a
53
0.5
0.5
0.05
0
vinylcyclopentene and
methylene group.[28]
a
cyclohexene with an exocyclic
100 (90)
0
Table 3. Au(I)-Catalyzed Skeletal Rearrangement of Enyne 13.[a]
[a] c = 0.2 M. [b] Conversion was determined by 1H-NMR analysis of the
crude product. Yield of the isolated product is given in parentheses. [c] x
mol% of [(Ph3P)AuCl] and x mol% of AgSbF6.
With 0.5 mol% of 3 (i.e., 1 mol% of Au) or 1 mol% of 4, full
conversion was not reached even after 20 h (entries 3 and 4) and
no reaction took place with complex 7 as the pre-catalyst (entry
5). On the other hand, complete and selective transformation of 9
into 10 was achieved with complex 8 (entry 6) with which a very
good 90% isolated yield of 10 was obtained at 1 mol% Au loading
(= 0.5 mol% of 8). Lowering the amount of 8 to 0.05 mol% caused
the reaction to stop (entry 7). Nevertheless, the excellent result
obtained with 0.5 mol% of this catalyst shows that the dissociation
of the dimeric precursor (or catalytic activation) is possible even
in a weakly coordinating solvent such as toluene. The robustness
of the active species also supports the idea of a formation-
recombination of the monomers that slows down the decay of the
catalyst.
Entry
[Au]
x
14:15
Conv [%][b]
[c]
1
2
3
4
5
[(Ph3P)AuCl]/AgSbF6
1
-
-
[c]
3
4
7
8
0.5
1
-
-
[c]
-
-
0.05
0.05
2.5:1
6.5:1
100 (64)[d]
100 (82)
[a] c = 0.2 M. [b] Conversions were determined by 1H-NMR analysis of the crude
product. The yield of the isolated product is given in parentheses. [c] Complex
mixture. [d] 3 h.
The hydroarylation of arenyne 11 was attempted next (Table
2).[8g,27] This reaction also requires a high temperature to proceed
satisfactorily (80 °C in 1,2-dichloroethane). Again, under such
conditions, only complex 8 afforded full conversion of 11 into 12,
which was isolated in a 92% yield (entry 5).
In the presence of [(Ph3P)AuCl]/AgSbF6, the reaction led to a
complex mixture, in which neither 14 nor 15 were observed (entry
1). Complexes 3 and 4 also proved active but unselective
catalysts, leading to complex mixtures of products among which
14 and 15 could be identified this time (entries 2 and 3).
Gratifyingly, the selectivity improved upon using 7 and 8 (entries
4 and 5). In the latter case, the reaction provided 14 as the major
product and the catalyst loading could be lowered to 0.05 mol%
Au, with still full conversion and an isolated yield of 82% (entry 5).
Table 2. Au(I)-Catalyzed Hydroarylation of Arenyne 11.[a]
The good activity of complex 8 in C–C bond forming reactions was
further demonstrated in the formal [4+2] cycloaddition of aryl
enyne 16 (Scheme 4).[29] The expected product 17 was isolated in
85% yield after 4 h at room temperature in 1,2-dichloroethane.
Entry
[Au]
x
Conv [%][b]
1
2
3
4
5
6
[(Ph3P)AuCl]/AgSbF6
1
15
3
4
7
8
8
0.5
1
8
21
0.5
0.5
0.05
10
100 (92)[c]
0
Scheme 4. Au(I)-Catalyzed [4+2] Cycloaddition of Enyne 16.
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Focusing next on C–O bond forming reactions, the superiority of
complex 8 over 3 and 4 was confirmed also for catalytic
rearrangement of propargyl acetate 18 to acetoxy allene 19 (in
1,2-dichloroethane at 20 °C, Table 4).[30] Even at a 0.1 mol% Au
loading (compared to 1 mol% for 3 and 4), complex 8 furnished
the rearranged product 19 in the highest isolated yield (88%, entry
3).
Lastly, the cyclization of alkynylfuran 22 into phenol 23 was
tested,[32] using only 0.05 mol% of 8 in 1,2-dichloroethane at room
temperature (Scheme 5). Even in this case, the desired
cyclization product was obtained with a good 70% isolated yield.
Table 4. Au(I)-Catalyzed Rearrangement of Propargyl Acetate
18.[a]
Scheme 5. Au(I)-Catalyzed Phenol Synthesis.
Conclusions
In this study, we have further explored the catalytic activity of a
rare type of the dimeric (3) and polymeric (4) gold(I) complexes
derived from 1’-(diphenylphosphanyl)-1-cyanoferrocene ligand.
These species showed moderate to low activity and selectivity in
the C–C bond forming reactions studied. On the other hand, they
efficiently catalyzed C–O bond forming transformations. This
family of gold complexes exhibiting hemilabile P,N-ligands was
extended by two new dimeric members (7 and 8), derived from 2-
(diphenylphosphanyl)benzonitrile. Complex 8 proved to be the
most versatile pre-catalyst in the series, catalyzing both C–C and
C–O bonds at 0.5 mol% and, in some case, even at 0.05 mol%
loadings. In particular, 8 proved very robust even at high
temperature and in the presence of water. While 8 differs from 7
only by the weaker coordinating nature of its counterion (SbF6- vs
Entry
[Au]
3
x
Yield [%][b]
1
2
3
0.5
1
76
56
88
4
8
0.05
[a] c = 0.2 M. [b] Yield of the isolated product is given.
Complexes 3, 4, 7 and 8 seemed virtually equally active when a
more strongly coordinating solvent was employed as the reaction
medium. When these complexes were applied to hydration of
alkyne 20 into ketone 21 in a MeOH/H2O mixture at 80 °C (Table
5, entries 2-5),[23a,31] each of these pre-catalysts provided the
ketone in a comparably high NMR yield (82-87%). However, in
the presence of 8, the reaction proved to be much faster. Again,
the [(Ph3P)AuCl]/AgSbF6 catalytic mixture was outperformed by
these new complexes (entry 1).
-
NTf2 ), its superiority could be explained by an easier
recombination of the two phosphanonitrile gold fragments since
the SbF6- anion leaves the Au+ ion free for coordination.
The collected results demonstrate successful implementation of
P,N-ligands in gold-catalysis, paving the way for a further catalytic
use of these air- and moisture-stable, readily accessible and
easy-to-handle complexes.
Table 5. Au(I)-Catalyzed Hydration of Alkyne 20.[a]
Experimental Section
General considerations. All manipulations were performed by standard
Schlenk techniques under an atmosphere of nitrogen or argon.
Compounds 5,[33] [AuCl(tht)],[34] 9,[8d] 11,[35] 13,[36] 16,[22b] 18,[37] and 22[32e]
were prepared according to the literature. Other chemicals were obtained
from commercial sources (Sigma-Aldrich, Alfa-Aesar). Dry and
deoxygenated dichloromethane was obtained from a PureSolv MD5
solvent purification system (Innovative Technology Inc., Amesbury, USA).
Solvents employed during chromatography and work-up were used
without any additional purification (reagent grade from Lachner, Czech
Republic).
Entry
[Au]
x
Yield [%][b]
1
2
3
4
5
[(Ph3P)AuCl]/AgSbF6
1
60
3
4
7
8
0.5
1
82
87
0.5
0.5
85[c],[e]
86[d],[e]
NMR spectra were recorded on Varian UNITY Inova 400 or on Bruker
AM250, AV300 or AV360 MHz spectrometers at 25 C. Chemical shifts are
given relative to internal tetramethylsilane (for 1H and 13C NMR) and to
external 85% aqueous H3PO4 (for 31P NMR). Electrospray ionization
mass spectra (ESI-MS) were obtained with a Bruker Esquire 3000
spectrometer. The samples were dissolved in HPLC-quality methanol.
Infrared spectra were measured on a Nicolet Magna 6700 FTIR instrument
[a] c = 0.2 M. [b] Determined by 1H-NMR analysis with p-anisaldehyde (1
equiv.) as an internal standard. [c] c = 0.5 M, 5 h. [d] c = 0.5 M, 1 h. [e]
isolated yields.
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in the range 400–4000 cm–1. Elemental analyses were determined with a
Perkin-Elmer PE 2400 Series II CHNS/O Elemental Analyzer.
in the same solvent (0.5 mL) and the reaction mixture was stirred at 110 °C
for 20 h. Then, the crude product was purified by flash column
chromatography using pentane/ethyl acetate (8:2) as the eluent to give
pure 10 (49.5 mg, 90%).[8d]
Preparation of [AuCl(5-κP)] (6). A solution of ligand 5 (574.6 mg, 2.0
mmol)
in
dichloromethane
(20
mL)
was
added
to
chloro(tetrahydrothiophene)gold(I) (641.2 mg, 2 mmol) dissolved in the
same solvent (20 mL). After stirring for 30 min, the clear reaction mixture
was filtered through a PTFE syringe filter (0.45 µm pore size) and
evaporated under vacuum. The solid residue was taken up with
dichloromethane (6 mL) and the solution was added into pentane (60 mL).
The precipitated product was isolated by suction, washed with pentane (3×
10 mL) and dried under vacuum. Yield: 1.02 g (98 %), colorless solid.
Synthesis of 12. To a solution of 8 (1.4 mg, 0.0010 mmol) in 0.5 mL of
1,2-dichloroethane was added a solution of arenyne 11 (52 mg, 0.020
mmol) in 0.5 mL of 1,2-dichloroethane. The reaction mixture was stirred at
80 °C for 1 h. Following evaporation under vacuum, the crude product was
purified by flash column chromatography using pentane/ethyl acetate (9:1)
as an eluent to give 12 (48 mg, 92%).38
Synthesis of 14 and 15. To a solution of 8 (0.7 mg, 0.0005 mmol) in 2.5
mL of 1,2-dichloroethane was added a solution of enyne 13 (215 mg, 0.960
mmol) in 2.5 mL of 1,2-dichloroethane. The reaction mixture was stirred at
room temperature for 1 h. Subsequent evaporation and flash column
chromatography using pentane/ethyl acetate (9:1) as the eluent afforded
a mixture of 14 and 15 (176 mg, 82%, 6.5:1).[39]
1H NMR (CD2Cl2): δ = 7.07-7.91 (m, C6H4PPh2) ppm. 31P{1H} NMR
(CD2Cl2): δ = 30.9 (s) ppm. IR (Nujol): max = 3053 m, 2681 w, 2225 m,
1906 w, 1827 w, 1589 w, 1570 w, 1341 w, 1318 m, 1194 w, 1135 w, 1101
s, 1068 w, 1028 w, 998 w, 878 w, 852, 756 m, 766 s, 714 m, 700 s, 693 s,
676 w, 619 w, 581 m, 581 m, 559 m, 546 s, 518 s, 503 s, 479 m, 447 w,
418 w cm−1. ESI+ MS: m/z = 542 ([6 + Na]+). Anal. calc. for C19H14NAuClP
(519.7): C 43.91, H 2.72, N 2.70%. Found. C 43.54, H 2.56, N 2.56%.
Synthesis of 17. To a solution of 8 (1.5 mg, 0.0011 mmol) in 0.5 mL of
1,2-dichloroethane was added a solution of enyne 16 (66 mg, 0.210 mmol)
dissolved in the same solvent (0.5 mL). The reaction mixture was stirred
at room temperature for 1 h. The crude product was purified by flash
column chromatography using Pentane/EtOAc 9:1 as eluent to give 17 (56
mg, 85%).[22b]
Synthesis
of
[Au2(µ(P,N)-5)2](NTf2)2
(7).
Solid
silver(I)
bis(trifluoromethanesulfonyl)imide (310.4 mg, 0.80 mmol) weighed on a
piece of broken glass was added to solution of 5 (415.7 mg, 0.80 mmol) in
dichloromethane (30 mL) and the resulting mixture was stirred for 30 min.
A small amount of Celite was added and the mixture was stirred for another
10 min before it was filtered through a syringe filer. The filtrate was diluted
with pentane (60 mL) and the mixture was evaporated under vacuum (N.B.
steps following halogen removal must be carried out as quickly as possible
because the solution is highly unstable). The separated product was dried
under vacuum and isolated as a colorless solid. Yield: 393 mg (64 %).
Synthesis of 19. To a solution of 8 (1.2 mg, 0.0008 mmol) in 4 mL of 1,2-
dichloroethane was added a solution of propargyl acetate 18 (370 mg, 1.61
mmol) in 4 mL of 1,2-dichloroethane. The reaction mixture was stirred at
room temperature for 1 h. The reaction mixture was evaporated and the
crude product was purified by flash column chromatography using
pentane/ethyl acetate (9:1) as the eluent to give 19 (325 mg, 88%).[23d]
1H NMR (CD2Cl2): δ = 7.06-7.96 (m, C6H4PPh2) ppm. 31P{1H} NMR
(CD2Cl2): δ = 27.4 (s) ppm. IR (Nujol): max = 2281 m, 1578 w, 1314 w,
1293 w, 1203 w, 1134 w, 1102 s, 1070 w, 1039 w, 1027 w, 998 m, 967 w,
890 w, 847 w, 799 w, 752 m, 722 m, 703 m, 692 m, 659 s, 617 w, 585 w,
533 m, 507 m, 495 m, 449 w cm−1. ESI+ MS: m/z = 502 ([Au(5) + H2O]+),
771 ([Au(5)2]+). Anal. calc. for C21H14N2AuF6O4PS2 (764.4): C 32.99, H
1.85, N 3.67%. Found. C 32.82, H 1.84, N 3.49%.
Synthesis of 21. To a solution of 8 (6.2 mg, 0.0043 mmol) in 1.8 mL of a
MeOH/H2O (2:1) mixture was added alkyne 20 (100 mg, 0.861 mmol). The
reaction mixture was stirred at 80 °C for 1 h. Evaporation followed by flash
column chromatography using pentane/ethyl acetate (95:5) as the eluent
provided analytically pure 21 (99 mg, 86%).[23a]
Synthesis of 23. To a solution of 8 (1.4 mg, 0.0010 mmol) in 5 mL of 1,2-
dichloroethane was added a solution of alkynylfuran 22 (300 mg, 2.0
mmol) in the same solvent (5 mL). The reaction mixture was stirred at room
temperature for 8 h. Then, the crude product was purified by flash column
chromatography using pentane/ethyl acetate (8:2) as the eluent to afford
pure 23 (210 mg, 70%).[31]
Synthesis of [Au2(µ(P,N)-5)2][SbF6]2 (8). Silver(I) hexafluoroantimonate
(171.8 mg, 0.50 mmol) weighed on a small piece of broken glass was
added to a solution of 5 (259.9 mg, 0.50 mmol) in dichloromethane (20
mL). After stirring for 30 min, the mixture was filtered through a PTFE
syringe filter (0.45 µm pore size) and directly added into pentane (80 mL).
The separated product was collected on a glass frit, washed with pentane
(3× 10 mL) and dried under vacuum. Yield: 340 mg (94 %), colorless solid.
Crystals suitable for X-ray diffraction analysis were grown by liquid-phase
diffusion of hexane into a dichloromethane solution of the complex.
Structure determination for 8. C38H28Au2F12N2P2Sb2, M = 1440.0 g mol–
1, colorless prism, 0.05  0.09  0.19 mm3, monoclinic, space group P21/c
(no. 14), a = 12.6656(4), b = 6.7301(2), c = 23.5378(7) Å;  = 99.751(1);
V = 1977.49(1) Å3, Z = 2, Dcalc = 2.42 g mL–1.
1H NMR (CD2Cl2): δ = 7.26-8.40 (m, C6H4PPh2) ppm. 31P{1H} NMR
(CD2Cl2): δ = 23.7 (s) ppm. IR (Nujol): max = 2281 m, 2067 sh, 1578 w,
1314 w, 1293 w, 1204 w, 1165 w, 1134 m, 1103 s, 1070 w, 1039 w, 1027
w, 998 w, 971 w, 890 w, 847 w, 800 w, 753 m, 703 w, 692 m, 659 s, 618
w, 585 w, 533 m, 507 w, 495 w, 450 w cm−1. ESI+ MS: m/z = 502 ([Au(5)
+ H2O]+), 771 ([Au(5)2]+). Anal. calc. for C19H14NAuF6PSb (720.0): C 31.69,
H 1.96, N 1.95%. Found. C 31.69, H 2.02, N 1.66%.
Full-set diffraction data (hkl) were recorded with a Bruker D8
VENTURE Kappa diffractometer equipped with a PHOTON100 detector,
IµS micro-focus sealed tube (Mo K radiation,  = 0.71073 Å) and a
Cryostream Cooler (Oxford Cryosystems) at 150(2) K. The data were
corrected for absorption (µ = 8.92 mm–1) using a numerical method
incorporated in the diffractometer software. A total of 17557 diffractions
was recorded (max = 27.5°, data completeness = 99.9%), from which 4541
were unique (Rint = 2.39%), and 4201 were observed according to the I >
2(I) criterion.
The physical and spectral data (1H NMR) for the following compounds are
in agreement with the data previously reported:
The structure was solved by direct methods (SHELXT[40]) and refined by
full-matrix least-squares routine based on F2 (SHELXL2014[41]). All non-
Synthesis of 10. To a solution of 8 (1.4 mg, 0.0010 mmol) in 0.5 mL of
toluene was added a solution of ene--ketoamide 9 (55 mg, 0.020 mmol)
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10.1002/cplu.201600562
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hydrogen atoms were refined with anisotropic displacement parameters.
The hydrogens were included in their calculated positions and treated as
riding atoms with Uiso(H) set to 1.2 Ueq(C) of their bonding carbon. The
refinement converged (/  0.001, 262 parameters) to R = 3.11% for the
observed, and R = 3.52%, wR = 7.57% for all diffractions. The final
difference electron density map displayed no peaks of chemical
significance, the relatively high extremes (max = 2.70, min = –1.60 e Å–
3) being attributable to crystal imperfections.
[7]
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A. S. K. Hashmi, Chem. Commun. 2016, 52, 6435.
CCDC-1514792 contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgements
This research was financially supported by MENESR, UPS, IUF,
CNRS and the Czech Science Foundation (project no. 13-
08890S).
Keywords: cyclizations • gold • homogeneous catalysis •
phosphane ligands • structure elucidation
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Entry for the Table of Contents
FULL PAPER
Bastien Michelet, David Lebœuf,
Christophe Bour, Karel Škoch, Filip
Horký, Petr Štěpnička,* Vincent
Gandon*
Page No. – Page No.
Catalytic Activity of Au(I) Complexes
with Hemilabile P,N-Ligands
Complexes of the type [Au2(µ(P,N)-L)2][X]2 (X = NTf2 or SbF6, L = 1’-
(diphenylphosphanyl)-1-cyanoferrocene or 2-(diphenylphosphanyl)benzonitrile) are
easy-to-handle and versatile precatalysts for various gold(I)-catalyzed reactions
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