Small Gold(I) and Gold(I)–Silver(I) Clusters by C?Si Auration

Article abstract of DOI:10.1002/chem.202001509

Auration of o-trimethylsilyl arylphosphines leads to the formation of gold and gold–silver clusters with ortho-metalated phosphines displaying 3c–2e Au?C?M bonds (M=Au/Ag). Hexagold clusters [Au₆L₄](X)₂ are obtained by reaction of (L?TMS)AuCl with AgX, whereas reaction with AgX and Ag₂O leads to gold–silver clusters [Au₄Ag₂L₄](X)₂. Oxo-trigold(I) species [Au₃O]⁺ were identified as the intermediates in the formation of the silver-doped clusters. Other [Au₅], [Au₄Ag], and [Au₁₂Ag₄] clusters were also obtained. Clusters containing PAu?Au?AuP structural motif display good catalytic activity in the activation of alkynes under homogeneous conditions.

Full text of DOI:10.1002/chem.202001509

Accepted Article
Accepted Article
Title: Small Gold(I) and Gold(I)-Silver(I) Clusters via C-Si Auration
Authors: Antonio M. Echavarren, Xiao-Li Pei, Ana Pereira, and
Ekaterina S. Smirnova
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1/2020

Chemistry - A European Journal
10.1002/chem.202001509
Small Gold(I) and Gold(I)-Silver(I) Clusters via C-Si Auration
Xiao-Li Pei, Ana Pereira, Ekaterina S. Smirnova, and Antonio M. Echavarren*
Abstract: Auration of o-trimethylsilyl arylphosphines leads to the
formation of gold and gold-silver clusters with ortho-metalated
phosphines displaying 3c-2e Au-C-M bonds (M = Au/Ag). Hexagold
these hexanuclear clusters show 3c-2e Au-C-M bonds (M =
Au/Ag)[ 13 ]. Under slightly different reaction conditions, other
polynuclear gold clusters have been also obtained by C-Si auration.
clusters [Au
whereas reaction with AgX and Ag
Au Ag ](X)
6 4 2
L ](X) are obtained by reaction of (L-TMS)AuCl with AgX,
2
O leads to gold-silver clusters
+
[
4
L
2 4
2
. Oxo-trigold(I) species [Au
3
O] were identified as the
intermediates in the formation of the silver-doped clusters. Other [Au
5
],
[
Au Ag], and [Au12Ag ] clusters were also obtained. Clusters containing
4
4
PAu-Au-AuP structural motif display good catalytic activity in the
activation of alkynes under homogeneous conditions.
Introduction
Aurophilicity has a fundamental importance on the wide structural
diversity of gold complexes and clusters,[1] as well as on their
photophysical properties[2] and their catalytic transformations.[3]
Small gold Au
n
clusters (n = 3-10) can catalyze different reactions[4]
and it has been proposed that small gold clusters can activate of
the C–H bond of methane.[5] However, polynuclear cationic Au(I)
entities remain nearly unexplored in gold catalysis. To date, only a
Scheme 1. a) C-B Auration to form hexanuclear gold clusters 2a.[11] b) C-Si
few catalytically active Au(I)
Thus, the group of Toste found that trinuclear oxonium gold cluster
(Ph PAu) O](BF ) is a catalyst for the cycloisomerization of 1,5-
allenyenes[
and our group reported that tetranuclear and
n
clusters (n ≥ 3) have been reported.
Auration of o-sylylphosphine gold(I) complexes 1 to form hexanuclear gold
clusters 2 of gold(I)-silver(I) clusters 3. L = PR , A = SbF .
2 6
Oxonium trigold cluster [Au
3
O]+ was found to be the key
[
3
3
4
6
]
intermediates in the formation of gold-silver clusters 3. Furthermore,
our studies reveal that clusters containing the PAu-Au-AuP
structural motif activate alkynes under homogeneous conditions,
presumably as a consequence of the presence of coordinatively
pentanuclear gold-silver clusters are active in the catalytic
carbonylation of amines under homogeneous conditions.[7]
Ligands play a crucial role in the engineering of gold
architectures and the tuning of their properties.[8] The strategy of
combining neutral phosphines and anionic ligands such as
thiolate/alkynyl ligands[9] has been gaining considerable attention
for the construction of hetero-ligated gold clusters, because the
higher affinity between gold and anionic fragments allows
accessing gold systems of high nuclearity. However, phosphines
with both multi-coordination ability and anionic property have been
less explored as ligands for the preparation of gold clusters.
labile gold(I), similar to gold cavities (pocket-like sites) that exist in
the well-studied [Au25] cluster.[3b,14]
Results and Discussion
The o-trimethylsilylaryl phosphine gold(I) complexes 1a-e were
prepared in 89-95% yields from the corresponding o-
[10]
trimethylsilylaryl phosphines and [Me
Complexes 1a-d react with 1 equiv AgSbF
form known 2a[11] as well as new hexanuclear gold clusters 2b-e,
2
SAuCl] in CH
2
Cl
2
at 23 °C.
Cl to
6
in MeOH-CH
2
2
We have described the synthesis of a single example of a
I
which were isolated as yellow or pale-yellow crystalline solids in
hexagold cluster via a Au /B transmetalation (Scheme 1a), which
52-81% yields (Scheme 2).[15]
The reaction of complex 1a with
different silver salts AgX (X = BF , OTf, NTf , NO ) led to the
corresponding [Au (L) ](X) clusters. However, other chloride
showed catalytic activity in some cycloisomerization of enynes.[11]
Now we have developed a more general method by auration-
assisted C-Si bond cleavage[12] from ortho-silylphosphines 1, which
4
2
3
6
4
2
scavengers such as Cu(OTf)
2
, Zn(OTf)
2
, In(OTf)
3
, TMSOTf, or
leads to hexanuclear gold(I) clusters [Au
different phosphine L ligands (Scheme 1b). Interestingly, when the
transmetalation was carried out in the presence of Ag O,
heteronuclear clusters [Au Ag ](SbF (3) were obtained. All
6 4 6 2
L ](SbF ) (2) bearing
Sc(OTf) ,
3
were not effective. When using NaBArF
4
the
corresponding hexanuclear gold species can be observed by 31P
NMR.
2
4
L
2 4
6 2
)
Complexes 1a-d derived from triaryl phosphines show singlets
in their 31P{ H} NMR spectra at 32.3-37.8 ppm in CD
1
Cl
, whereas
2
2
[
] Dr. X.-L. Pei, Dr. A. Pereira, Dr. E. S. Smirnova, Prof. A. M. Echavarren
the corresponding signals for dialkylarylphosphine and di(2-
Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of
Science and Technology, Av. Països Catalans 16, 43007 Tarragona (Spain)
Departament de Química Analítica i Química Orgànica, Universitat Rovira i
Virgili, C/ Marcel·li Domingo s/n, 43007 Tarragona (Spain)
furyl)arylphosphine gold(I) complexes 1e and 1d were observed at
4
7.10 and -5.12 ppm, respectively. The resulting hexanuclear
clusters showed their 31P signals shfted downfield by 8-24 ppm: 2a-
E-mail: aechavarren@iciq.es
Supporting information for this article is available on the WWW under
http://www.angewandte.org or from the author
c (44.6-48.2), 2d (71.50), and 2e (3.15).
New clusters 2b-e were characterized by X-ray diffraction,
showing a pseudo-octahedral geometry with six gold atoms
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Chemistry - A European Journal
10.1002/chem.202001509
stabilized by only four formally anionic-phosphine ligands, different
from the hexanuclear gold clusters.[16,17] Compared to aurophilic
interactions of 2.706(4)–3.351(4) Å found in 2a,[11] the Au–Au
bonds lie in the range of 2.689(7)–3.162(8) Å in 2b, 2.718(6)–
C
6
H
4
MeP)
6
Au
6
](NO
3
)
2
.[17] The ligand coordination in 3a and 3b is
very different. In cluster 3a, four gold atoms are linked together by
the R P group and the aryl rings, displaying the same coordinating
mode as in hexagold(I) analogues 2a-e. The structure of 3b is more
distorted and can be viewed as the fusion of two binuclear gold
complexes bridged by two silver atoms by Au-Ag interactions.
2
3.352(6) Å in 2c, 2.726(4)–3.325(4) Å in 2d, and 2.709(2)–3.341(2)
Å in 2e, respectively. In clusters 2b-c, two naphthyl groups stabilize
the gold atoms in the 3c–2e Au–C–Au bonds, while two phenyl
groups are involved in the 3c–2e bonds in clusters 2d-e. The
average C–Au–C angles in 2b (159.6(6)°) and 2c (162.1(4)°) are
slightly bigger than those of 2a (159.1(3)°). In clusters 2d and 2e,
the average C–Au–C angles are 157.8(3)° and 162.2°,
respectively.[15]
Clusters 4a and 4c display doublets at 46.5 and 40.3 ppm,
respectively in the 31P{ H} NMR spectra, whereas 3a and 3b show
triplets at 52.2 and 55.8 ppm, respectively.
1
2+
A-2
2+ A-2
Ar
Ar
Ar
Ar
R
R
Au
Ag
Ag
L
L
L
L
P
S
2+
A-2
Au-Cl Ag O
L
A
u
L
acetone
2
Ar
L
Au
Au
Au Au
Ag
Ar
AgSbF6
Au
Ar
Au
Ar
SiMe3
Au
Au
A
g
S
1a-c
L
Au
3a,b
R
R
Ar
Ar
L
L
Ar
Ar
P
AgSbF6 (1 equiv)
L
4a,c
Au-Cl
Au
Au
Ar
MeOH, CH2Cl2, 25 ºC, 0.5 h
L
Au
SiMe3
Ar
1
1
1
1
1
a: Ar = C6H4, R = Ph
2a: Ar = C6H4, L = PPh2 (65%)
2
b: Ar =1,2-C10H6, R = Ph
2b: Ar = µ2-1,2-C10H6, L = PPh2 (81%)
2c: Ar = µ2-2,1-C10H6, L = PPh2 (52%)
2d: Ar = C6H4, L = PCy2 (65%)
2
c: Ar= 2,1-C10H6, R = Ph
d: Ar = C6H4, R = Cy
e: Ar = C6H4, R = 2-Fur
2e: Ar = H, L = P(2-Fur)2 (55%)
4a (59%)
4c (66%)
2b
2c
3a (72%)
3b (49%)
4+
A’ -
4
L
L
Au
Au
Ag
Ag
2
Scheme 2. Hexanuclear gold clusters 2a-e, obtained by C-Si auration from 1a-e.
A = SbF . Fur: furyl. 1,2-C10 and 2,1-C10 derived from 1-diphenylphosphino-
-trimethylsilylnaphthalene and 2-diphenylphosphino-1-trimethylsilylnaphthalene,
d
2e
L Au
Au L
Au
Au
O
6
H
4
H
4
O
2
Au
Au
L
Au
Au L
respectively. Counteranions and solvent molecules and omitted for clarity.
Ag
Ag
Au
Au
Reaction of 1a with excess of silver(I) salts did not result in the
L
L
formation of gold-silver clusters. However, addition of excess
5a’
L = PPh2)
(
6 2 2 2
AgSbF to a suspension of 1a and 1 equiv of Ag O in CH Cl led to
the formation of heterometallic cluster 4a (Scheme 3). Notably,
cluster 4a rearranges in the presence of acetone to form cluster 3a,
in which each of the silver atoms coordinates with a molecule of
acetone. Similar behaviour was observed in acetonitrile or
methanol. Upon removal of the coordinating solvent under vacuum,
Scheme 3. Hexanuclear gold-silver clusters 3a,b, 4a,c, and 5a’ by C-Si auration
in the presence of Ag O. A = SbF , A’ = NTf . Counteranions and solvent
molecules and omitted for clarity.
2
6
2
Hexadecanuclear heterometallic cluster 5a was obtained as a
byproduct in the preparation of 4a (Scheme 3). This cluster was
3
3
a was slowly converted into 4a. Two related gold-silver clusters
b and 4c were also obtained and structurally characterized. In the
better obtained from a complex [(L)Au(NEt
by reaction of 1a with AgSbF in the presence of excess NEt
Treatment of 1a’ in CH Cl containing excess water with AgSbF
3 6
)](SbF ) 1a’, prepared
6
3
.
silver-doped hexanuclear gold-silver clusters 4a and 4c, silver
atoms substitute the two axial positions, forming 3c-2e Au-C-Ag
bonds.[15] Due to the argentophilic interactions in 4a and 4c (ca. 2.9
Å), the hexanuclear heterometallic cores are distributed as a
distorted octahedrons with edge-sharing bi-tetrahedral geometry,
similar to the structure of hexanuclear nanogold cluster [(p-
2
2
6
(
2 equiv) led to 5a in 47% yield. Cluster 5a’ was prepared similarly
using AgNTf instead of AgSbF . The structure of 5a´ shows 3c-2e
Au-C-Au and Au-C-Ag bonds, as well as an interesting μ -O
coordinating mode, which to the best of our knowledge,
2
6
4
2-
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Chemistry - A European Journal
10.1002/chem.202001509
corresponds to the highest-nuclei oxo-bridged gold-silver
assembly among the known oxo-gold clusters.[15,18]
6 2 2 2
upon addition of AgSbF to a mixture of 1a and Ag O in CD Cl , a
new species corresponding to 9a was formed, which reacted
further to finally form 4a (Scheme 5). Oxonium gold cluster 9a was
isolated as white solid and its structure was confirmed by mass
spectrometry (m/z 1609.2049). Starting from 1d, a similar oxonium
trigold(I) complex 9d was obtained, whose structure was
determined by X-ray diffraction.[15,22]
6 2
Interestingly, treatment of 1c with NaSbF and Ag O led to
pentanuclear gold(I) cluster 6 in 69% yield,[ 19 ] along with
pentanuclear gold(I)-silver(I) 7 as a minor product (ca. 5%)
(
0
Scheme 4). Cluster 7 could be obtained from 1c in 57% yield using
.25 equiv AgSbF
.[15] Moreover, digold complex[15, 20 ] 8 was
obtained by reaction of 1c with AgOAc through the initial formation
of neutral [LAu(OAc)]. The addition of excess AgSbF to a solution
led quantitively to the formation of cluster 4c.
6
Presumably, reaction of 1a-d complexes with AgX salts leads
+
-
6
to complexes [(L-TMS)Au(S)] X , which immediately evolve to form
of 8 in CH
2
Cl
2
hexanuclear gold(I) clusters 2a-d. On the other hand, when the
2
reactions are performed in the presence of Ag O, oxonium trigold
complexes 9 are formed as intermediates, which are less reactive
in the C-Si auration and, as a result, can incorporate silver(I)
leading to the formation of gold(I)-silver(I) clusters.
+
A-
Hexagold clusters 2a-d are stable in solution. Thus, cluster 2a
was recovered unchanged upon recrystallization in acetonitrile as
well as after being heated at 80 °C in 1,2-dichloroethane for 24 h.
Thermogravimetric analysis shows that clusters 2a, 2e, 3a, and 4a
only undergo decomposition in the solid state at high temperatures
Au
Au
L
Au
Au
L
L
Au
L
(230-270 °C).[23] However, treatment of 2a with PPh
in CH Cl led
+
A-
3 2 2
6
: L = PPh2 (69%)
[19]
to the formation of a known digold complex similar to 8. In the
case of pentagold cluster 6, the 31P NMR signals became broad in
acetonitrile solution, although 6 was recovered unchanged after
crystallization in this solvent.
Ag O (1 equiv)
NaSbF6 (3 equiv)
CH Cl , 25 ºC, 3 h
2
2
2
Ag
Au
Au
L
L
Ph Ph
P
Au
Au
i) Ag O (1 equiv),
L
Table 1. Addition of aromatic and heteroaromatic nucleophiles to 1,6-enyne 19
to form 20a-c catalyzed by gold or gold-solver clusters.
2
Au-Cl
CH Cl , 25 ºC, 0.5 h
2
2
L
SiMe3
ii) AgSbF6 (0.25 equiv)
MeOH, 25 ºC, 0.5 h
1c
7: L = PPh2 (57%)
AgOAc(1 equiv)
MeOH, CH Cl
2
2
25 ºC, 1.5 h
Entry
NuH
Catalyst
Time (h)
11a-c (yield, %)[a]
1
2
3
4
ArH
2a
2a
2a
2b
20
20
16
12
11a (76)
11b (40)
11c (76)
11a (71)
IndH
MeIndH
ArH
5
6
7
8
9
ArH
ArH
ArH
IndH
MeIndH
ArH
ArH
ArH
ArH
ArH
ArH
ArH
ArH
ArH
ArH
2c
2d
2e
2e
2e
4a
3a
3b
4c
12
12
3.3
8
11a (87)
11a (3)
8
(50%)
7
11a (98, 95[b]
11b (79)
11c (67)
11a (98)
11a (97)
11a (99)
11a (96)
11a (< 1)
11a (99)
-[d]
)
Scheme 4. Clusters 6-8 obtained from gold(I) complex 2c.
Counteranions and solvent molecules and omitted for clarity.
6
A = SbF .
8
+
A-
Me3Si
10
11
12
4
R2P
4.5
9
Au
Ag2O
O
1a,d
Au
Au
AgSbF6
PR2
13
6.5
12
12
12
12
24
3.5
P
R2
SiMe3
Me3Si
1
1
1
4
6
9
9
a (R = Ph)
d (R = Cy)
5[c]
6 + NaBArF
4
AgSbF6
LAu4Ag2](SbF6)2 (4a)
9d
6
7
[
1 [
7
c]
7 + NaBArF
-[d]
4
6
Scheme 5. Oxonium gold intermediates 9a,b from 1a,d. A = SbF . Counteranions
and solvent molecules and omitted for clarity.
18
8
-[d]
19
5a[e]
11a (93)
We confirmed that the reaction of [Ph
AgSbF gives oxonium gold cluster [O(AuPPh
suggests that similar oxonium gold complexes might be involved
as intermediates in the formation of the gold-silver clusters. Indeed,
3
PAuCl] with Ag
),[21] which
](SbF
6
2
O and
[a] Yield and product rations determined by 1H NMR using 1,3,5-
tris(trifluoromethyl)benzene as internal standard. [b] Isolated yield. [c] Reaction in
the presence of NaBAr 4 (10 mol%). [d] < 1% yield. [e] catalyst loading 0.05%.
6
3
)
3
F
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Chemistry - A European Journal
10.1002/chem.202001509
The catalytic activity of the new clusters was studied in the
addition of 1,3,5-trimethoxybenzene, indole, and N-methylindole to
To probe our hypothesis that the catalytically active site is the
central gold atom in the PAu-Au-AuP structural motifs, we also
1
,6-enyne 10 to give cycloadducts 11a-b regio- and
examined the reactivity of known full-phosphine-protected gold and
[24]
[16a]
6 4
[Au Ag
C],[16b] nanogold clusters
stereoselectively (Table 1). Clusters 2a-e showed activities in the
order 2e > 2c > 2a ≈ 2b > 2d (Table 1, entries 1-9). These results
correlate with the electronic and steric properties of the ligands,
since 2-furyl group in 1e is the most electron-withdrawing and less
bulky phosphine substituent. Remarkably, 1 mol% of cluster 2e led
to 11a in 95% yield in ca. 3 h (Table 1, entry 7), showing a catalytic
activity comparable to that displayed by a bulky phosphite gold(I)
complex (5 mol%, 2 h, 66% yield),[24] which is one of the most
reactive gold(I) complexes used routinely in the activation of
alkynes. The catalyst loading with 2a and 2d could be decreased
to 0.05 mol% maintaining good conversions.[23] Cluster 2e was also
found to be the most reactive[23] for the formation of indenes from
gold-silver clusters [Au
6
C],
[ 28 ]
nano-[Au
6
][19] and [Au13].
However, none of these species
displayed catalytic activity in the addition of 1,3,5-
trimethoxybenzene to 1,6-enyne 10 at 25 °C.[23]
Conclusions
In summary, we have found that the auration of trimethylsilyl
phosphines leads to the formation of well-defined small gold and
gold-silver containing 3c-2e Au-C-M (M = Au/Ag) bonds. On the
other hand, when the chloride abstraction of complexes [(L-
TMS)AuCl] was performed with AgSbF
hexanuclear gold-silver clusters [Au
6
in the presence of Ag
Ag
]2+ were obtained.
O] acts as the intermediate
in this silver-doping process, which takes place due to a slower C-
Si auration process. Other clusters [Au ], [Au Ag], [Au ] and
] have also been obtained. The activity of these small gold
2
O,
7
-phenylethynyl cycloheptatriene,[ 25 ] and for the formal [4+2]
4
2
[26]
+
intramolecular cycloaddition of arylalkynes with alkenes.
Trinuclear oxonium gold species [Au
3
Clusters 3a,b and 4a,c display higher catalytic activity than the
corresponding hexagold congeners probably due to the structure
effect by silver doping[27] (Table 1, entries 10-11). In contrast, the
5
4
2
[
Au12Ag
4
clusters has been studied in typical Au(I)-catalyzed reactions of
enynes. Remarkably, hexanuclear gold cluster 2e with
difurylphosphine ligand displays a reactivity similar or even higher
than other commonly used mononuclear gold catalysts.
reaction with cluster 6 led only to traces of 11a (Table 1, entry 14)
although the reactivity could be restoredin the presence of NaBArF
Table 1, entry 15), while NaBArF
by itself does not promote this
transformation. However, cluster 7 was unreactive even in the
presence of NaBArF
(Table 1, entries 16 and 17). Digold complex
showed no reactivity (Table 1, entry 18). Hexadecanuclear
,
4
(
4
4
Acknowledgements
8
We thank MINECO/FEDER, UE (CTQ2016-75960-P), H2020-
Marie Sklodowska-Curie contract to X.-L.P. (Grant Agreement:
747170), the AGAUR (2017 SGR 1257), and CERCA
Program/Generalitat de Catalunya for financial support. We thank
Shaofei Ni for the optimization of the structure of 9a by DFT
calculations and Mauro Mato for helpful discussions. We also thank
the ICIQ X-ray diffraction unit for the crystallographic analysis.
4
cluster 5a [Au12Ag ] also displays good activity (0.05 mol%, 3.5 h,
9
3% yield of 20a) (Table 1, entry 19). Similar catalytic activity was
[
23]
found with enynes bearing internal alkynes.
Homometallic gold clusters 2a-c, 2d, and 6 did not undergo
decomposition when the corresponding reactions in Table 1 were
monitored by 31P NMR spectroscopy.[23] On the other hand, the
gold(I)-silver(I) clusters underwent slow decomposition, which
might explain why heteronuclear clusters 4a and 4c, which present
only PAu-Ag-AuP motifs, are also catalytically active (Table 1,
entries 10 and 13). In these cases, as suggested by 31P NMR,
decomposition or structural rearrangement of 4a and 4c to
generate an active gold(I) species probably takes place in solution.
2
Keywords: Gold clusters · Silver clusters · Gold catalysis · C(sp )-
Si auration • Metalophilic interactions
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1]
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Chemistry - A European Journal
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