Coinage Metal (Bisfluorosulfonyl)imide Complexes: Preparation, Characterization, and Catalytic Applications

Article abstract of DOI:10.1002/ejic.201901058

Triflate (^–OTf) and triflimide (^–NTf₂) represent two most widely used weakly coordinating counteranions in transition metal catalysis, yet their high price hinders large-scale application. Herein, we report the preparation, characterization, and catalytic applications of silver(I), gold(I), and copper(II) (bisfluorosulfonyl)imide (^–FSI) complexes, showing ^–FSI as a low cost alternative of ^–OTf and ^–NTf₂. These complexes, including AgFSI·2MeCN (1), AgFSI·MeCN (2), AgFSI·H₂O (3), (AgFSI)₆·(H₂O)₄ (4), AgFSI (5), LAuFSI (6a–6e), and CuFSI₂·4H₂O (7), are prepared conveniently starting from KFSI, an inexpensive chemical, and shown interesting structural features and some unprecedented coordination modes. In comparison with the corresponding coinage metal triflimides, the FSI complexes have exhibited comparable or better catalytic performance in a series of the model chemical transformations.

Full text of DOI:10.1002/ejic.201901058

DOI: 10.1002/ejic.201901058
Full Paper
Coinage Metal Complexes | Very Important Paper |
Coinage Metal (Bisfluorosulfonyl)imide Complexes: Preparation,
Characterization, and Catalytic Applications
Yu Tang[a] and Biao Yu*[a]
Abstract: Triflate (–OTf) and triflimide (–NTf2) represent two (4), AgFSI (5), LAuFSI (6a–6e), and CuFSI2·4H2O (7), are prepared
most widely used weakly coordinating counteranions in transi- conveniently starting from KFSI, an inexpensive chemical, and
tion metal catalysis, yet their high price hinders large-scale appli- shown interesting structural features and some unprecedented
cation. Herein, we report the preparation, characterization, and coordination modes. In comparison with the corresponding coin-
catalytic applications of silver(I), gold(I), and copper(II) (bisfluoro- age metal triflimides, the FSI complexes have exhibited compara-
sulfonyl)imide (–FSI) complexes, showing –FSI as a low cost ble or better catalytic performance in a series of the model
alternative of –OTf and –NTf2. These complexes, including chemical transformations.
AgFSI·2MeCN (1), AgFSI·MeCN (2), AgFSI·H2O (3), (AgFSI)6·(H2O)4
Introduction
and high energy consuming process. Thus, developing inexpen-
sive counteranions and exploiting their metal complexes as cat-
alysts comparable to or even better than the corresponding
metal triflates and triflimides becomes an important task for
the future development and application of transition metal ca-
talysis.[11]
The choice of a proper counteranion is critically important in
the development of a successful transition metal catalyst,[1]
which influences the structure and catalytic activity of the cata-
lyst,[2,3] and the kinetics[4] and selectivity of the catalyzed reac-
tions.[5,6] Compared to the various types of ligands developed,
the types of counteranions that are commonly employed in
transition metal catalysis are limited.[1a,1f,7] Among these coun-
teranions, anions based on the [E(SO2RF)n]– motif (where E = O,
N, or C), especially triflate (–OSO2CF3 or –OTf) and triflimide
(–N(SO2CF3)2 or –NTf2), represent the most widely used types of
counteranions (Figure 1).[8,9] In the category of weakly coordi-
nating counteranions, –OTf and –NTf2 have many advantages in
terms of high stability, low nucleophilicity and easy availability.
A large number of transition metal-catalyzed reactions devel-
oped during the past two decades employed OTf or NTf2 as
the counteranion of the catalysts in the optimal catalytic
systems,[9] which were usually established after extensive
screening of a series of catalysts with difference only in the
counteranions. Despite the excellent performance and numer-
ous applications of metal triflates and metal triflimides as cata-
lysts, a major and inherent drawback of these counteranions
lies in their high cost.[10] The production of triflic acid (HOTf)
and triflylimide (HNTf2), the starting reagents for the prepara-
tion of metal triflates and triflimides, requires electrochemical
fluorination to introduce the -CF3 moiety,[8] which is a high-cost
–
–
Figure 1. Representative counteranions based on the [E(SO2RF)n]– motif and
the present work.
–
(Bisfluorosulfonyl)imide (–N(SO2F)2 or FSI) anion was firstly
reported by Ruff in 1965,[12] but has received little attention
during the subsequent four decades.[13,14] Recently, alkali metal
FSI salts, i.e., MFSI (M = Li, Na, K), has received an increasing
attention as energy storage materials,[15] which have been pro-
duced on industrial scale and become the inexpensive commer-
cial FSI source. Other types of the FSI derivatives have so far
been reported scarcely.[16] Thus, trimethylsilyl (bisfluorosulfon-
yl)imide (TMSFSI) has found applications as Lewis acid catalyst
in a few organic transformations.[17] Transition metal FSI com-
plexes, other than Ruff's sliver(I) FSI complexes, have not yet
been exploited. In 2014, Sharpless and Dong et al. reported
a new click reaction based on sulfur(VI) fluoride exchange.[18]
Recently, they disclosed a stable fluorosulfuryl imidazolium
salt,[19] showing that the sulfonyl fluoride motif is considerably
stable under various conditions. In continuation of our own re-
search on the gold(I)-catalyzed glycosylation reaction,[20] we en-
[a] State Key Laboratory of Bioorganic and Natural Products Chemistry,
Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic
Chemistry, University of Chinese Academy of Sciences,
Chinese Academy of Sciences,
345 Lingling Road, Shanghai 200032, China
E-mail: byu@sioc.ac.cn
http://biaoyu.sioc.ac.cn
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejic.201901058.
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–
visaged that replacing OTf or –NTf2 with FSI in the commonly have been reported recently, wherein the counteranions are
used gold(I) catalysts might be able to reduce the cost and usually –NTf2 or –OTf.[22] Complex 1 represents the first low
improve the efficiency.
melting silver-containing ionic liquid bearing FSI as the counter-
anion.
Summarized in Figure 2 are some basic aspects of the FSI
motif.[12,21] The current procedure for the large-scale prepara-
tion of FSI salts is through the reaction of alkali metal (bischlo-
rosulfuryl)imide salt with KF in apolar solvent (such as CH2Cl2)
at reflux temperature,[21] which is a much safe and economical
process than the electrochemical fluorination required for the
preparation of triflate and triflimide salts. The pKa of HFSI in
water at 25 °C is 1.28, whereas the corresponding HNTf2 is 1.7,
indicating that –FSI has weaker basicity and coordination ability
than –NTf2. Stability is another important property of a counter-
anion to be used in catalysis, and –FSI shows satisfactory stabil-
ity in aqueous solutions, which remains stable in neutral or
acidic solutions and proceeds slow hydrolysis in 30 % aqueous
KOH at 100 °C. With these salient features, we expected that
transition metal FSI complexes would have potentials as a new
type of catalysts. Herein, we report the synthesis, characteriza-
tion, and catalytic applications of coinage metal FSI complexes.
Scheme 1. Synthesis of AgFSI(MeCN)n complexes 1 and 2.
Complex 1 was readily dissolved in CH2Cl2, evaporation of
the solvent followed by vacuum drying to constant weight af-
forded colorless crystals. The structure of the resulting crystals
was identified to be AgFSI·MeCN (2) by single-crystal X-ray anal-
ysis (CCDC 1909180), and was also supported by gravimetric,
elemental, and NMR analysis. In the crystals (Figure 3), half of
the Ag(I) ions are coordinated by two MeCN molecular in a
linear nitrogen-bound fashion, while the other half of Ag(I) ions
are coordinated by two FSI anion in a linear nitrogen-bound
fashion. Ag(I) disulfonylamide acetonitrile complexes have been
synthesized and characterized by Jones and Blaschette et al.[23]
Four coordination modes were observed in these previous
complexes; Ag(I) ion could be coordinated by up to four MeCN
molecules or to two linear disulfonylamides.[23] The structure of
Figure 2. Some basic aspects of the FSI compounds.
Results and Discussion
Synthesis and Characterization of Silver(I) FSI Complexes
In Ruff's original work,[12] Ag(I) FSI complexes were prepared
by reaction of HFSI and Ag2O in CF3COOH or benzene. Several
drawbacks exist in this procedure: HFSI is corrosive and not yet
commercially available, and the solvent used is also corrosive
or toxic. We thus sought to develop a new method to prepare
Ag(I) FSI complexes. The alkali metal FSI salts are now commer-
cially available and the potassium salt is the cheapest one. Solu-
bility test indicated that KFSI easily dissolved in MeCN while
KNO3 is insoluble in MeCN. We thus planed to prepare Ag(I) FSI
complexes through metathesis reaction of KFSI and AgNO3 in
MeCN. To our delight, mixing a MeCN solution of KFSI with an
equimolar MeCN solution of AgNO3 led to immediate precipita-
tion of KNO3, which was removed by filtration. Evaporation of
the resulting colorless solution followed by vacuum drying to
constant weight afforded a colorless liquid, which was identi-
fied to be AgFSI(MeCN)2 (1) by gravimetric, elemental, and NMR
analysis (Scheme 1). Surprisingly, complex 1 remained as a liq-
uid even at –30 °C. In fact, several silver-containing ionic liquids
Figure 3. Crystal structure of complex 2 at 30 % probability ellipsoids
(hydrogen atoms are omitted for clarity).
Scheme 2. Synthesis of Ag(I)FSI hydrates 3 and 4.
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Figure 4. (A) Crystal structure of complex 4 at 30 % probability ellipsoids. (B) Coordination modes of the Ag(I) ions (the outer-sphere Ag(I) atoms and hydrogen
atoms are omitted for clarity).
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complex 2 represents a new coordination mode in Ag(I) di- thus Ag(I) cation rarely coordinates directly with water in crystal
sulfonylamides nitrile complexes. The Ag–N bond length in the structures.[26] In fact, nearly all crystalline inorganic silver salts
previous MeCN-Ag(I) cation range from 209.5 to 232.6 pm, are anhydrous with few exceptions, such as AgClO4 and AgF,
while in complex 2, the length is 210.5(4) pm. The Ag–N bond and complex 4 represents a rare example of well characterized
length in disulfonylamides coordinated Ag(I) ion range from hydrated inorganic Ag(I) salt. Herein, the in-depth characteriza-
212.7 to 230.0 pm, and in complex 2, the length is 220.2(3) pm. tion of this complex yet fascinating structure furthers our un-
In both MeCN and disulfonylamides dicoordinated Ag(I) ion, the derstanding of the coordination interaction of the FSI anion
angles of N–Ag–N are 180°. Linear two acetonitrile coordinated with coinage metal ions.
Ag(I) ion has previously been observed in Ag(I) complex
[Ag(NCCH3)2][B{C6H3(CF3)2}4] by Kühn et al.[24] Two slightly dif-
Table 1. Selected bond lengths [pm] and angles (°) for the six coordination
ferent linear coordination geometry was observed, the Ag–N
bond length are 209.7(2) pm and 206.6(4) pm, and the angles
of N–Ag–N are 180°, similar to that in complex 2. Very interest-
ingly, in those complexes, the C–N–Ag angles are 171.9(3)° and
177.2(2)°, indicating a slightly bent geometry, while in complex
2 the C–N–Ag angles are 179.9(4)°, indicating that the two
MeCN ligand and Ag(I) ion are arrayed in a perfect linear geom-
etry.
modes of Ag(I) ions in complex 4.
Both complexes 1 and 2 were easily dissolved in water, evap-
oration of the solvent followed by vacuum drying to constant
weight afforded colorless crystals, which were identified to be
AgFSI·H2O (3) by gravimetric, elemental, and NMR analysis
(Scheme 2). It is noteworthy that the hydrate forms of AgFSI
and AgNTf2 have not been reported previously,[25] and complex
3 represents the first AgFSI hydrate characterized to date.
A sample of complex 3 was sealed in a flask and stayed at
room temperature for 6 months, colorless block shaped crystals
and a clear solution were formed. The crystals were collected
and determined to be (AgFSI)6·(H2O)4 (4), which represents the
first AgFSI hydrate characterized by X-ray diffraction analysis
(CCDC 1909185).
Shown in Figure 4 is the crystal structure of complex 4,
which is rather complex, containing six types of Ag(I) ions in
six different coordination modes (modes 1–6). Selected bond
lengths and angles are summarized in Table 1. In these struc-
tures, the Ag(I) ion are five-, six-, or seven-coordinated. Four
types of Ag(I) ions (modes 1, 2, 4, and 6) are bridged by two
μ2-oxygen of water ligands to form an unprecedented dimeric
core [Ag2(μ2-H2O)2]2+ structure,[25] and the remaining coordina-
tion sites are coordinated by the FSI anion acting as O-donor
or N-donor ligand. Interestingly, in mode 4, the FSI anion acts
an F-donor ligand (Ag–F distance 273.75 pm),[27] highlighting
the versatile coordination behavior of FSI anion as a multiden-
tate O, N, or F ligand. In the remaining two non-water coordina-
tion modes (modes 3 and 5), each Ag(I) ion is coordinated by
four FSI anions acting as bidentate O-donor or monodentate N-
donor, and only slight differences are observed between these
two modes. The Ag–N bond lengths of the Ag–FSI coordination
structure in di-nitrogen coordinated modes 3 and 5 range from
241.6(12) to 244.3(13) pm, longer than in mono N-coordinated
mode 1 [228.1(14) pm] and mode 6 [232.6(15) pm], whereas in
complex 2 the distance is 220.2(3) pm. The N–Ag–N angles are
nearly perpendicular (89.7° in mode 3 and 92.0° in mode 5);
such a perpendicular two N-coordination mode has not been
With hydrate 3 in hand, we attempted to prepare anhydrous
AgFSI through dehydration. Heating hydrate 3 in air at 105 °C
for 2 h led to partial decomposition, as observed by NMR. After
many attempts, we managed to remove the water molecule in
hydrate 3 by azeotropic distillation with toluene followed by
vacuum drying to constant weight (Scheme 3). The water con-
observed in coinage metal NTf2 complexes. In silver chemistry, tent in the prepared sample could be measured by 1H NMR
it is well known that the coordination interaction between the analysis in CD3CN using internal standards and no external wa-
soft Ag(I) cation and the hard water ligand is relatively low,[28] ter signal was observed. Several grams of the anhydrous AgFSI
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(5) were prepared via this procedure. Compared to the original
route for the preparation of AgFSI complexes, the present pro-
cedure is safe and convenient, and suitable for large-scale prep-
aration.
Scheme 3. Preparation of anhydrous AgFSI (5).
The stability of the above prepared Ag(I)FSI complexes were
evaluated. AgFSI·(MeCN)2 (1), AgFSI·MeCN (2), and (AgFSI)6·
(H2O)4 (4), were found stable at room temperature under air
atmosphere for a long time; heating these complexes to 100 °C
led to slow decomposition. Anhydrous AgFSI (5) was very hy-
groscopic and should be stored under dry and inert atmos-
phere. The aqueous solution of AgFSI was rather stable at room
Scheme 4. Synthesis of ligand-stabilized gold(I)FSI complexes 6a–e.
temperature; in fact, an aqueous solution of AgFSI (0.082
M)
remained intact in a brown reagent bottle for 6 months as
measured by 19F-NMR.
Ad3PAuCl[32] with AgNTf2 and raised single crystals for X-ray dif-
fraction analysis (CCDC 1909394). Thus, a full comparison of
the structures of the present FSI complexes with their –NTf2
counterparts became possible, and the representative bond
lengths (pm) and angles (°) are listed in Table 2.
Synthesis and Characterization of Ligand Stabilized Gold(I)
FSI Complexes
Having established a convenient approach to the preparation
It is observed that both the Au–P (or Au–C in complex 6e)
of the Ag(I) FSI complexes, we set out to prepare ligand stabi- and Au–N bonds in the FSI complexes are slightly shorter (0.5–
–
lized gold(I) FSI complexes. A straightforward procedure for the 1.4 pm) than in the corresponding NTf2 series, indicating that
preparation of this type of complexes would via reaction of the coordination of FSI anion to the Au center is stronger that
ligand stabilized gold(I) chlorides with the anhydrous AgFSI (5). the –NTf2 anion. Near linear two-coordination mode of Au(I)
Indeed, treatment of chloro(triphenylphosphine)gold(I) with 5 center are observed in complexes 6a, 6e, and 6e′, whereas in
led to the corresponding Ph3PAuFSI complex (6a) in high yield. complexes 6a′, 6b, 6b′, 6c, and 6c′, a slightly bent geometry
However, a major drawback of this procedure lies in the incon- are observed that the bond angles of P–Au–N range from
venience in handing the hygroscopic anhydrous silver salt 5. 173.03(16)° to 176.45(17)°. A dramatic difference of coordination
To avoid this problem, we attempted to use air-stable Ag(I)FSI geometry between complex 6e and 6e′ is observed; in complex
acetonitrile complexes 1 or 2 as the FSI precursor. To our de- 6e′, the planes of the –NTf2 anion (S–N–S plane) and NHC ligand
light, mixing a CH2Cl2 solution of complex 1 or 2 with an equi- (N–C–N plane) are nearly coplanar,[29b] whereas in complex 6e,
molar CH2Cl2 solution of LAuCl led to immediate precipitation these planes are nearly perpendicular. This interesting phenom-
of AgCl; filtration and evaporation of the solvent afforded the enon might be caused by the C–H···F interaction of the F atom
LAuFSI complexes. Gravimetric, elemental, and NMR analysis in- in the FSI anion with the methyl group of the adjacent IPr li-
dicated that an equimolar MeCN always existed in the product, gand in complex 6e. The F–H distance is 227.58 pm, indicating
which could not be removed by vacuum drying or coevapora- a strong C–H···F interaction,[33] whereas in 6e′, no such interac-
tion with hexane. Gratifyingly, evaporation of the crude samples tion is observed. This dramatic difference clearly demonstrates
in a mixture of CH2Cl2 and toluene (v/v = 2:1) led to the corre- the distinct coordination properties of FSI anion compared to
sponding acetonitrile-free products, as confirmed by NMR anal- its fluoroalkyl disulfonylamides counterparts.
ysis. Using this method, ligand-stabilized gold(I) FSI complexes
6a–e were prepared in high yields (Scheme 4).
We have previously studied the coordination of water with
LAu+ cation, which could be conveniently measured by 1H NMR
Complexes 6a, 6b, 6c, and 6e were readily crystallized from in that the coordination led to a downfield shift of the water
a mixture solvent of CH2Cl2/hexane, whereas complex 6d was signal. We found that for LAuOTf complexes hydration was a
highly soluble. The X-ray crystal structures of complexes 6a ready process, while for LAuNTf2 complexes the hydration proc-
(CCDC 1909182), 6b (CCDC 1909184), 6c (CCDC 1909183), and ess was greatly inhibited by the strong coordination of Au(I)
6e (CCDC 1909181) are shown in Figure 5. In these complexes, with the nitrogen.[20e] Herein, the behavior of LAuFSI complexes
the gold(I) center is nearly linear coordinated by a FSI anion in aqueous solutions was examined. In fact, the water signal in
and the phosphine or NHC ligand. The –NTf2 counterparts the solution of complexes 6a–6e all occurred at 1.55 ppm, close
(6a′–e′) of 6a,[29a] 6c,[30] and 6e[29b] have been characterized by to “free” water signal (1.52 ppm in CD2Cl2), suggesting that the
X-ray diffraction analysis, while that of 6b (i.e., 6b′) has not.[31] coordination of LAu+ cation and FSI anion was hardly inter-
We newly prepared 6b′ (Ad3PAuNTf2) through the reaction of rupted by water.
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Figure 5. Crystal structures of LAuFSI complexes 6a, 6b, 6c, 6e, and LAuNTf2 complex 6b′ at 30 % probability ellipsoids (hydrogen atoms are omitted for
clarity).
Table 2. Representative bond lengths [pm] and angles (°) in the LAuFSI and
LAuNTf2 complexes.
through metathesis of Ag(I) FSI complex 1 with CuCl2 in water
(Scheme 5). The reaction proceeded smoothly as indicated by
the immediate precipitate of AgCl. Filtration followed by evapo-
ration and vacuum drying afforded Cu(II) FSI complex 7 as blue
crystals. The structure of this complex was unambiguously char-
acterized to be Cu(FSI)2·4H2O by X-ray diffraction analysis
(CCDC 1909186, Scheme 5).
In the crystal structure of complex 7, the Cu(II) ion is coordi-
nated by four water molecules and two FSI anions in an elon-
gated tetragonal octahedral geometry.[36] Four water molecules
are at the corner of the square plane, with two Cu(II)–O bond
lengths at 195.4(4) pm and two at 195.1(4) pm, and O–Cu(II)–O
angles at 92.24(17)° and 177.6(2)°. The two nitrogen atoms of
the FSI anions are weakly coordinated with the Cu(II) center at
distant axial positions, with Cu(II)–N distances at 253.56(60) and
Synthesis and Characterization of Copper(II) FSI
Complexes
Copper(II) salts bearing weakly coordinating counteranions,
such as CuSO4 and Cu(OTf)2, have been widely used as pre-
catalyst in transition metal catalysis.[34] The commercially avail-
able Cu(II)(NTf2)2, firstly reported by Sonoda et al. in 1997, ex-
hibited excellent catalytic activities in several copper catalyzed
reactions.[35] With the well characterized Ag(I) FSI complexes in 270.31(60) pm. It is noted that Cu(II) dimesylamide tetra-
hand, we investigated the preparation of Cu(II) FSI complexes hydrates Cu[N(SO2CH3)2]·4H2O has been synthesized and char-
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Scheme 5. Synthesis and crystal structure of Cu(II) FSI complex 7.
acterized by Blaschette and Jones et al.,[37] which consists of
a centrosymmetric trans-octahedral molecule and is similar to
complex 7. However, the (CH3SO2)2N– anion acts as a mono-
dentate O-donor rather than N-donor. This dramatic difference
demonstrates again the distinct coordination properties of FSI
anion as compared to its alkyl disulfonylamides counterparts.
The stability of CuFSI2·4H2O (7) was evaluated. Either the
crystals of this complex or its aqueous solution remained stable
at room temperature for several weeks, while heating to 100 °C
led to slow decomposition. A blue crystal sample of complex 7
was stored at room temperature for 3 months, the sample
turned to white-blue fuming slurry and a new signal was ob-
served in 19F NMR spectrum (δ = 55.4 ppm in H2O). Thus, it is
recommended that this complex should be used in time.
Catalytic Applications
The catalytic performance of the above synthesized coinage
metal FSI complexes, in comparison to that of the known coin-
age NTf2 complexes, were examined in a variety of model reac-
tions. The preliminary results are summarized in Scheme 6.
The gold(I)-catalyzed organic transformations have been de-
veloped rapidly in the past two decades, wherein the ligand
stabilized Au(I)NTf2 complexes become one of the most widely
used gold(I) catalysts.[38,39] The propargyl ester hydration reac-
tion, originally reported by Shi et al.,[40] has been selected as a
benchmark for the evaluation of gold(I) catalysis, wherein nitro-
gen ligand stabilized gold(I) catalyst such as 6a′ exhibited opti-
mal performances.[40] A comparison between the catalytic per-
formances of 6a and 6a′ in this reaction at 1.26 mmol scale
Scheme 6. Catalytic applications of the coinage metal FSI complexes.
under identical conditions revealed similar catalytic activity donor (10ꢀ). Indeed, the different counteranions in the catalysts
(Scheme 6, Reaction A).
brought about a slightly different α/ꢀ selectivities. Such a differ-
ence reflects again the involvement of the counteranion in the
glycosylation reactions,[20b,20d] which warrants further studies.
The catalytic potential of the Au(I)FSI complexes was further
We next chose gold(I)-catalyzed glycosylation of glycosyl o-
alkynylbenzoates as a model reaction, which was developed by
our group and has found wide applications.[20,41] The glycosyl-
ation reactions of perbenzyl glucopyranosyl o-alkynylbenzoate examined in two more gold(I)-catalyzed reactions (Reactions C
10α/10ꢀ and adamantanol 11 proceeded smoothly in the pres- and D). The gold(I)-catalyzed electrophilic aromatic substitution
ence of either complex 6a or 6a′, delivering the glycoside prod- with α-diazoester represents an efficient C–C bond forming re-
uct 12 in high yields (93 %–100 %) as a mixture of α- and ꢀ- action via gold-carbenoids, and complex 6d′ has been identi-
anomers (Scheme 6, Reaction B). The use of the α-donor (10α) fied as an optimal catalyst.[42] A comparison between the cata-
favored the formation of the ꢀ product (12ꢀ), in contrast, the lytic performance of 6d and 6d′ in the reaction of diazoester 13
α product (12α) was favorably formed when starting with the ꢀ with phenol derivative 14 under otherwise identical conditions
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revealed that complex 6d exhibited slightly better catalytic ac- as their NTf2 counterparts (6a′-6c′); however, in IPrAuFSI (6e),
–
tivity than the conventional 6d′ (72 % vs. 66 %). The intermolec- the planes of the NTf2 anion (S–N–S plane) and NHC ligand
ular cyclization of ynamides and propargylic carboxylates cata- (N–C–N plane) are nearly perpendicular, whereas in IPrAuNTf2
lyzed by 6e′, developed by Hashmi et al.,[43] provided a facile (6e′), these two planes are nearly coplanar. In Cu(FSI)2·4H2O (7),
method for the preparation of highly substituted cyclopentadi- the Cu(II) ion is coordinated by four water molecules and two
enes. A comparison between the catalytic performance of 6e FSI anions in an elongated tetragonal octahedral geometry.
and 6e′ at 1.25 mmol scale under otherwise identical conditions These distinct coordination properties of FSI anion compared
revealed that complex 6e exhibited slightly better catalytic ac- to that of –NTf2 (and other fluoroalkyl disulfonylamides) indi-
tivity than 6e′ (69 % vs. 64 %; Reaction D). The outcomes of cates FSI anion as a potentially unconventional weakly coordi-
these two reactions demonstrate that FSI complexes could be nating counteranion in transition metal chemistry. Brief evalua-
better catalysts than the corresponding NTf2 complexes which tion of these complexes in a series of Au(I), Ir(III)/Ag(I), and Cu(II)
have been used previously.
catalyzed reactions has revealed that the FSI complexes could
serve as efficient and versatile catalysts. Compared to the
widely used coinage metal NTf2 catalysts, the FSI catalysts are
cost-effective, readily accessible, and exhibit comparable or
slightly better catalytic performances. With these promising fea-
tures, this series of fundamentally important FSI complexes
shall find wide applications in the future development of transi-
tion metal chemistry.
Various transition metal NTf2 complexes are commonly pre-
pared through halide abstraction of the corresponding metal
halides with AgNTf2.[44] The application of Ag(I) FSI complexes
as halide abstractor was thus investigated. The Ir(III)-catalyzed
C–H hydroarylation with 2-pyridyl group as a directing group
was selected as a model reaction (Reaction E).[45] Previous stud-
ies revealed that the optimal counteranion for this reaction
was –NTf2, which was introduced by halide abstraction of
[IrCp*Cl2]2 (Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl) with
AgNTf2. The Ag(I)FSI complexes, including AgFSI·2MeCN (1),
AgFSI·MeCN (2), and AgFSI, together with AgNTf2, were exam-
ined herewith. Under the previously established optimal condi-
tions, comparable yields and ratios of the hydroarylation prod-
ucts 20 and 21 were obtained (ca. 36 % for 20 and ca. 15 % for
21) when Ag(I)FSI complexes 1, 2, or 5 were employed; the
yields of 20 were slightly better than that with AgNTf2 (30 %
for 20).
Experimental Section
General. The syntheses of coinage metal FSI complexes were pre-
formed under ambient atmosphere unless specialized. Analytical
grade commercial reagents were used without further purification
unless specialized. Thin layer chromatography (TLC) was performed
on TLC Silica Gel 60 F254 (Merck). The TLC plates were visualized
with UV light and/or by staining with EtOH/H2SO4 (8 %, v/v). Flash
column chromatography was performed on Silica Gel 60 (40–64 μm,
Fluka, Canada). NMR spectra were measured on Varian Mercury 300,
Bruker AM 400, NEO 500 and Agilent 500 MHz NMR spectrometer
at 25 °C. 1H and 13C NMR signals were calibrated to the residual
Finally, the catalytic potential of Cu(II)FSI complex 7 was
tested, with per-O-acetylation of glucose being chosen as a
model reaction (Reaction F). Yadav et al. have screened a variety
of Cu(II) salts as catalysts for this reaction and found proton and carbon resonance of the solvent (CDCl3: δH = 7.26 ppm;
Cu(ClO4)2·6H2O to be the optimal.[46] In the presence of 1.0 mol-
δC = 77.16 ppm or CD2Cl2: δH = 5.32 ppm; δC = 54.00 ppm). Elemen-
tal analysis was obtained on a Vario EL III elemental analyzer.
% Cu(ClO4)2·6H2O, the reaction completed within 0.5 h to pro-
vide per-O-acetyl glucose 23 in 97 % yield. Many other Cu(II)
complexes, such as Cu(OAc)2·H2O, Cu(NO3)2·3H2O, CuCl2·2H2O,
and CuSO4·5H2O led to poor results. To our delight,
CuFSI2·4H2O (7) was found to be an efficient catalyst for this
reaction, which completed in 14 h in the presence of 1.0 mol-
% of 7 to give 23 in 95 % yield.
X-ray Crystallography
Single crystal X-ray data were collected on Bruker Apex II CCD dif-
fractometer operating at 50 kV and 30 mA using Mo Kα radiation
(λ = 0.71073 Å) at 133 K.
CCDC 1909180 (for 2), 1909185 (for 4), 1909182 (for 6a), 1909184
(for 6b), 1909183 (for 6c), 1909181 (for 6e), 1909394 (for 6b′), and
1909186 (for 7) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre.
Conclusion
We have developed convenient procedures for the preparation
of a series of the coinage metal FSI complexes, those include
Synthesis of AgFSI·2MeCN (1). To a mixture of KFSI (6.529 g,
29.8 mmol) and AgNO3 (5.059 g, 29.8 mmol) in a 250 mL round-
AgFSI·2MeCN (1), AgFSI·MeCN (2), AgFSI·H2O (3), (AgFSI)6·- bottomed flask equipped with a Teflon-coated magnetic stir bar
was added MeCN (HPLC grade, 80 mL). The mixture was stirred for
1 h, and then filtered through a sand core funnel (G4 type with 3–
4 μm cores). The resulting KNO3 cake was washed with MeCN (HPLC
grade, 20 mL × 2). The filtrate was combined and concentrated in
vacuo to afford a colorless liquid, which was further dried under
high vacuum to constant weight to afford complex 1 as a colorless
liquid (10.99 g, 99.7 % yield). 1H NMR (500 MHz, CD2Cl2): δ = 2.23
(s, 6H). 13C NMR (126 MHz, CD2Cl2): δ = 119.74, 2.83. 19F NMR
(282 MHz, CD2Cl2): δ = 49.32 (s). Elemental analysis calcd. (%) for
C4H6AgF2N3O4S2: C 12.98, H 1.63, N 11.35; found C 13.34, H 2.02,
(H2O)4 (4), AgFSI (5), LAuFSI (6a–6e), and Cu(FSI)2·4H2O (7).
Novel and interesting structural features and coordination
modes were observed in these complexes. In the crystal of
AgFSI·MeCN (2), half of the Ag(I) ions are coordinated by two
MeCN in a linear fashion while the other half of Ag(I) ions are
coordinated by two FSI anion in a linear nitrogen-bound fash-
ion. (AgFSI)6·(H2O)4 (4) contains six types of Ag(I) ions in six
different coordination modes (modes 1–6), wherein –FSI can be-
have as bidentate O-donor, monodentate N-donor, or even F-
donor. The R3PAuFSI complexes (6a–6c) show similar geometry N 11.49.
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Synthesis of AgFSI·MeCN (2). Complex 1 (852 mg, 2.30 mmol) was
dissolved in CH2Cl2 (20 mL), the resulting solution was filtered and
concentrated in vacuo to afford a colorless liquid, which was further
dried under high vacuum to constant weight to afford complex 2
as colorless crystals (755 mg, 99.7 % yield). 1H NMR (500 MHz,
CD2Cl2): δ = 2.25 (s, 3H). 13C NMR (126 MHz, CD2Cl2): δ = 119.94,
2.84. 19F NMR (282 MHz, CD2Cl2): δ = 49.45 (s). Elemental analysis
calcd. (%) for C2H3AgF2N2O4S2: C 7.30, H 0.92, N 8.51; found C 7.74,
H 1.40, N 8.09.
modified literature procedure.[32] A THF (100 mL, freshly distilled)
solution of Ad3P (400 mg, 0.916 mmol) was added dropwise to a
stirred CH2Cl2 (25 mL) solution of Me2SAuCl (400 mg, 1.36 mmol)
in a 250 mL round-bottomed flask under argon atmosphere. The
mixture was stirred at r.t. for 30 min, and then concentrated under
reduced pressure to half volume. EtOH (150 mL) was added, and
the product participated as white solids. The mixture was filtered
and washed with EtOH (15 mL) to afford a white powder, which
was suspended in MeOH (60 mL) and stirred for 1 h. The mixture
was filtered and dried under reduced pressure to afford a white
powder (452 mg). 397 mg of the powder was suspended in a CH2Cl2
(5.0 mL) and petroleum ether (7.5 mL) was added. The mixture
was filtered and dried under reduced pressure to afford
Ad3PAuCl·CH2Cl2 (378 mg, 0.50 mmol) as a white powder. The over-
Synthesis of AgFSI·H2O (3). Complex 1 (4.290 g, 11.60 mmol) was
dissolved in deionized H2O (40 mL) under sonication. The resulting
solution was concentrated in vacuo and again dissolved in deion-
ized H2O (40 mL). The solution was concentrated in vacuo and fur-
ther dried under high vacuum to constant weight, affording com-
plex 3 as a white solid (3.60 g, 100 % yield): 19F NMR (282 MHz,
H2O) δ = 49.31 (s); elemental analysis calcd. (%) for AgF2H2NO5S2 H
0.66, N 4.58, found H 0.88, N 4.55.
1
all yield based on Ad3P is 62 %. H NMR (300 MHz, CDCl3) δ = 5.30
(s, 2H), 2.40 (s, 18H), 2.04 (s, 9H), 1.74 (q, J = 13.0 Hz, 18H).
To
a mixture of complex 1 (34.6 mg, 93.5 μmol) and
Isolation and Characterization of (AgFSI)6·(H2O)4 (4). Complex 3
was stored in a 100 mL round-bottomed flask for 6 months, color-
less block shaped crystals and colorless solution were formed. The
crystals were isolated and characterized by X-ray diffraction analysis
to be (AgFSI)6·(H2O)4 (complex 4): 19F NMR (282 MHz, H2O) δ =
49.31 (s).
Ad3PAuCl·CH2Cl2 (70.5 mg, 93.5 μmol) in a 25 mL round-bottomed
flask equipped with a Teflon-coated magnetic stir bar was added
CH2Cl2 (5.0 mL). The mixture was stirred for 15 min and filtered
through a sand core funnel (G4 type with 3–4 μm cores). The result-
ing AgCl precipitate was washed with CH2Cl2 (2 mL × 2). The filtrate
was combined, toluene (2 mL) was added and the resulting solution
was concentrated in vacuo to afford a white solid, petroleum ether
(2.0 mL) was added, and the resulting mixture was concentrated in
vacuo and then dried under high vacuum to constant weight to
Synthesis of AgFSI (5). Complex 1 (878 mg, 2.37 mmol) was dis-
solved in deionized H2O (15 mL) under sonication in a 50 mL round-
bottomed flask. The resulting solution was concentrated in vacuo
and again dissolved in deionized H2O (10 mL). The solution was
concentrated in vacuo and further dried under high vacuum to
afford a white solid, toluene (25 mL) was added and the mixture
was distilled under atmospheric pressure using a Dean–Stark appa-
ratus to remove water. After all the water was removed, the result-
ing mixture was cooled to room temperature and concentrated in
vacuo to afford a white solid, which was further dried under high
vacuum at 100 °C for 2 min to afford anhydrous AgFSI (5) as a
white solid (718 mg, theoretical amount: 683 mg). Salt 5 was very
hygroscopic and should be stored under dry and inert atmosphere.
1H NMR analysis of a CD3CN solution of 5 using 1-bromo-4-iodo-
benzene as internal standard indicated that the sample contains
trace amount of toluene, and no external water could be detected.
19F NMR (282 MHz, CD3CN) δ = 45.90; elemental analysis calcd. (%)
for AgF2NO4S2 N 4.86, found N 4.44.
1
afford complex 6b as a white solid (76.5 mg, 100 % yield): H NMR
(500 MHz, CD2Cl2) δ = 2.41 (br, 18H), 2.06 (br, 9H), 1.83–1.70 (m,
18H); 13C NMR (126 MHz, CD2Cl2) δ = 47.95 (d, J = 17.1 Hz), 43.44
(br), 36.73, 29.69 (d, J = 8.4 Hz); 19F NMR (471 MHz, CD2Cl2) δ =
53.71 (s); 31P NMR (202 MHz, CD2Cl2) δ = 82.67 (s); elemental analy-
sis calcd. (%) for C30H45AuF2NO4PS2 C 44.28, H 5.57, N 1.72, found
C 44.28, H 5.64, N 1.47.
Synthesis of Ad3PAuNTf2 (6b′). To a mixture of AgNTf2 (24.6 mg,
63.4 μmol) and Ad3PAuCl (42.5 mg, 63.5 μmol) in a 25 mL round-
bottomed flask equipped with a Teflon-coated magnetic stir bar
was added CH2Cl2 (5.0 mL). The mixture was stirred for 15 min and
filtered through a sand core funnel (G4 type with 3–4 μm cores).
The AgCl precipitate was washed with CH2Cl2 (2 mL × 2). The filtrate
was combined and concentrated in vacuo to afford complex 6b′ as
1
a white solid (54.6 mg, 94 % yield): H NMR (500 MHz, CD2Cl2) δ =
Synthesis of Ph3PAuFSI (6a). To a mixture of Complex 1 (91.3 mg,
2.40 (br, 18H), 2.06 (br, 9H), 1.84–1.67 (m, 18H); 13C NMR (126 MHz,
0.247 mmol) and Ph3PAuCl (122.0 mg, 0.247 mmol) in a 25 mL CD2Cl2) δ = 119.89 (q, J = 322.8 Hz), 47.93 (d, J = 16.3 Hz), 43.49
round-bottomed flask equipped with a Teflon-coated magnetic stir
bar was added CH2Cl2 (2.0 mL). The mixture was stirred for 15 min
and filtered through a sand core funnel (G4 type with 3–4 μm
cores). The resulting AgCl precipitate was washed with CH2Cl2
(2 mL × 2). The filtrate was combined, toluene (2 mL) was added
and the resulting solution was concentrated in vacuo to afford a
white solid, which was further dissolved in CH2Cl2 (4.0 mL), and
petroleum ether (2.0 mL) was added. The resulting solution was
concentrated in vacuo and then dried under high vacuum to con-
stant weight to afford complex 6a as a white solid (155 mg, 98.7 %
(br), 36.74, 29.69 (d, J = 8.2 Hz); 19F NMR (471 MHz, CD2Cl2) δ =
–76.36 (s); 31P NMR (202 MHz, CD2Cl2) δ = 81.96 (s); elemental analy-
sis calcd. (%) for C32H45AuF6NO4PS2 C 42.06, H 4.96, N 1.53, found
C 40.43, H 4.91, N 1.51.
Synthesis of Au2(FSI)2(μ-DPPF) (6c). To a mixture of complex 1
(74.0 mg, 0.200 mmol) and Au2Cl2(μ-DPPF) (102.0 mg, 0.200 mmol)
in a 25 mL round-bottomed flask equipped with a Teflon-coated
magnetic stir bar was added CH2Cl2 (2.0 mL). The mixture was
stirred for 15 min and filtered through a sand core funnel (G4 type
with 3–4 μm cores). The resulting AgCl precipitate was washed with
CH2Cl2 (2 mL × 2). The filtrate was combined, toluene (1 mL) was
added and the resulting solution was concentrated in vacuo to af-
ford an orange solid, which was then dried under high vacuum to
constant weight to afford complex 6c as an orange solid (131.6 mg).
1H NMR analysis revealed that the product contains ca. 0.4 eq co-
crystallized toluene (correspond to 3 % w/w), which could not be
removed by washing with petroleum ether and high vacuum dry-
ing. The yield is thus calcd. 97 %. 1H NMR (500 MHz, CD2Cl2) δ =
1
yield). H NMR (500 MHz, CD2Cl2): δ = 7.65–7.47 (m, 15H). 13C NMR
(126 MHz, CD2Cl2): δ = 134.72 (d, J = 13.8 Hz), 133.22 (d, J = 2.8 Hz),
130.13 (d, J = 12.4 Hz), 127.68 (d, J = 66.7 Hz). 19F NMR (282 MHz,
CD2Cl2): δ = 51.24 (s). 31P NMR (121 MHz, CD2Cl2): δ = 31.27 (s).
Elemental analysis calcd. (%) for C18H15AuF2NO4PS2: C 33.81, H 2.36,
N 2.19; found C 33.62, H 2.36, N 2.22.
Synthesis of Ad3PAuFSI (6b)
Complex 6b was prepared by the reaction of complex 1 and
Ad3PAuCl·CH2Cl2, the latter was synthesized according to a slightly 7.67–7.39 (m, 20H), 4.85 (s, 4H), 4.30 (s, 4H); 13C NMR (126 MHz,
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CD2Cl2) δ = 133.91 (d, J = 14.3 Hz), 133.21, 129.97 (d, J = 12.2 Hz),
12.5:1) to give 9[40] (233 mg, 96 % for 6a and 229 mg, 94 % for
1
128.69 (d, J = 68.0 Hz), 76.66, 76.65 (d, J = 8.0 Hz), 75.21 (d, J = 6a′) as a colorless oil: H NMR (300 MHz, CDCl3) δ = 7.46–7.35 (m,
13.4 Hz); 19F NMR (471 MHz, CD2Cl2) δ = 53.98 (s); 31P NMR
(202 MHz, CD2Cl2) δ = 25.53 (s); elemental analysis calcd. (%) for
C34H28Au2F4FeN2O8P2S4 C 31.21, H 2.16, N 2.14, found C 31.58, H
2.32, N 1.99.
5H), 5.97 (s, 1H), 2.19 (s, 3H), 2.11 (s, 3H).
Reaction B: Gold(I)-catalyzed glycosylation reaction. To a mix-
ture of 10α or 10ꢀ (150 mg, 0.206 mmol), 11 (25.0 mg, 0.164 mmol),
and 5Å MS was added dry CH2Cl2 under argon atmosphere. The
mixture was stirred at r.t. for 1 h and then cooled to 0 °C, Au(I)
catalyst (13.4 mg 6a or 15.5 mg 6a′, 21.0 μmol, 10 mol-%) was
added, and the reaction mixture was stirred at 0 °C for 2 h, TLC
indicated the reaction was complete. The solvent was removed un-
der reduced pressure and the residue was purified by flash chroma-
tography on silica gel (petroleum ether/ethyl acetate = 30:1 to 20:1
to 17:1) to give 12[47] as a white solid, the yields and α/ꢀ ratio were
shown in Scheme 6. Data of product 12 prepared starting from 10ꢀ
catalyzed by 6a: 1H NMR (500 MHz, CDCl3) δ = 7.41–7.23 (m, 30.1H),
7.22–7.19 (m, 1.95H), 7.17–7.14 (m, 1.89H), 5.30 (d, J = 3.6 Hz, 1.00H),
5.02 (t, J = 10.5 Hz, 2.01H), 4.93 (d, J = 10.9 Hz, 1.10H), 4.87–4.81
Synthesis of (Ar*O)3PAuFSI (6d). To a mixture of complex 1
(37.2 mg, 0.101 mmol) and (Ar*O)3PAuCl[42] (88.4 mg, 0.101 mmol)
in a 25 mL round-bottomed flask equipped with a Teflon-coated
magnetic stir bar was added CH2Cl2 (5.0 mL). The mixture was
stirred for 15 min and filtered through a sand core funnel (G4 type
with 3–4 μm cores). The resulting AgCl precipitate was washed with
CH2Cl2 (2 mL × 2). The filtrate was combined, toluene (2 mL) was
added and the resulting solution was concentrated in vacuo to af-
ford a white foam, which was then dissolved in CH2Cl2 (2 mL), petro-
leum ether (5.0 mL) was added. The resulting mixture was concen-
trated in vacuo and then dried under high vacuum to constant
weight to afford complex 6d as a white foam (104.4 mg, 100 % (m, 2.83H), 4.79 (d, J = 10.9 Hz, 1.08H), 4.76–4.69 (m, 3.68H), 4.65
1
yield): H NMR (500 MHz, CD2Cl2) δ = 7.49 (dd, J = 2.5, 1.5 Hz, 2H),
(d, J = 12.1 Hz, 1.10H), 4.63–4.54 (m, 3.09H), 4.50–4.44 (m, 1.96H),
7.39 (dd, J = 8.5, 1.6 Hz, 2H), 7.20 (dd, J = 8.6, 2.5 Hz, 2H), 1.44 (s,
4.07–4.00 (m, 1.90H), 3.81–3.72 (m, 2.12H), 3.70–3.60 (m, 3.84H),
27H), 1.30 (s, 27H); 13C NMR (126 MHz, CD2Cl2) δ = 149.50, 147.61 3.59–3.42 (m, 4.21H), 2.21–2.10 (m, 5.41H), 2.00–1.92 (m, 2.99H),
(d, J = 6.7 Hz), 139.87 (d, J = 6.8 Hz), 126.34, 124.90, 119.82 (d, J =
1.91–1.79 (m, 8.07H), 1.70–1.56 (m, 11.44H); 13C NMR (126 MHz,
CDCl3) δ = 139.20, 138.83, 138.72, 138.55, 138.50, 138.46, 138.34,
9.1 Hz), 35.53, 35.16, 31.58, 30.82; 19F NMR (471 MHz, CD2Cl2) δ =
53.76 (s); 31P NMR (202 MHz, CD2Cl2) δ = 90.83 (s); elemental analy- 138.24, 128.49, 128.47, 128.46, 128.42, 128.40, 128.35, 128.26,
sis calcd. (%) for C42H63AuF2NO7PS2 C 49.26, H 6.20, N 1.37, found
C 49.72, H 6.28, N 1.30.
128.10, 128.07, 128.01, 127.96, 127.86, 127.83, 127.78, 127.70,
127.69, 127.66, 127.58, 127.57, 96.38, 89.97, 85.26, 82.48, 82.22,
80.23, 78.36, 78.28, 75.83, 75.66, 75.43, 75.22, 75.04, 74.70, 74.66,
73.57, 73.49, 72.98, 69.81, 69.66, 68.92, 42.93, 42.59, 36.43, 30.84,
30.79.
Synthesis of IPrAuFSI (6e). To a mixture of complex 1 (101.1 mg,
0.273 mmol) and IPrAuCl (170.0 mg, 0.273 mmol) in a 25 mL round-
bottomed flask equipped with a Teflon-coated magnetic stir bar
was added CH2Cl2 (3.0 mL). The mixture was stirred for 15 min and
filtered through a sand core funnel (G4 type with 3–4 μm cores).
The resulting AgCl precipitate was washed with CH2Cl2 (2 mL × 2).
The filtrate was combined, toluene (2 mL) was added and the result-
ing solution was concentrated in vacuo to afford a white solid,
which was then dried under high vacuum to constant weight to
afford complex 6e as a white solid (204.0 mg, 97 %): 1H NMR
(500 MHz, CD2Cl2) δ = 7.57 (t, J = 7.8 Hz, 2H), 7.35 (d, J = 7.8 Hz,
4H), 7.32 (s, 2H), 2.50 (hept, J = 6.9 Hz, 4H), 1.31 (d, J = 6.9 Hz, 12H),
Reaction C: Gold(I)-catalyzed electrophilic aromatic substitu-
tion with α-diazoester. To a mixture of 13 (177 mg, 1.0 mmol), 14
(610 mg, 5.0 mmol), and wet CH2Cl2 (5.0 mL) in a 25 mL round
bottomed flask was added Au(I) catalyst (51.2 mg 6d or 56.0 mg
6d′, 50.0 mmol, 5.0 mol-%) under air atmosphere. The reaction mix-
ture was stirred at r.t. for 1 h, TLC indicated the reaction was com-
plete. The solvent was removed under reduced pressure and the
residue was purified by flash chromatography on silica gel (petro-
leum ether/ethyl acetate = 100:0 to 50:1) to give 15[42] (195 mg,
1.23 (d, J = 6.9 Hz, 12H); 13C NMR (126 MHz, CD2Cl2) δ = 167.68, 72 % for 6d and 178 mg, 66 % for 6d′) as a colorless oil: 1H NMR
146.26, 134.00, 131.47, 124.82, 124.57, 29.40, 24.42; 19F NMR (300 MHz, CDCl3) δ = 7.33–7.25 (m, 5H), 6.82 (s, 1H), 6.76 (s, 1H),
(471 MHz, CD2Cl2) δ = 53.33 (s); elemental analysis calcd. (%) for
C27H36AuF2N3O4S2 C 42.35, H 4.74, N 5.49, found C 42.18, H 4.75, N
5.46.
5.93 (s, 2H), 4.95 (s, 1H), 3.74 (s, 3H).
Reaction D: Gold(I)-catalyzed intermolecular cyclization of
ynamides and propargylic carboxylates. To a mixture of 8
(217.2 mg, 1.25 mmol) and 16 (331.5 mg, 1.25 mmol) in dry CH2Cl2
Synthesis of Cu(FSI)2·4H2O (7). To a mixture of complex 1 (3.70 g,
10.0 mmol) and CuCl2 (672 mg, 5.0 mmol) in a 100 mL round- (10.0 mL) was added Au(I) catalyst (48.0 mg 6e or 54.0 mg 6e′,
bottomed flask equipped with a Teflon-coated magnetic stir bar
was added deionized H2O (40 mL). The mixture was stirred for 1 h,
and filtered through a sand core funnel (G4 type with 3–4 μm
cores). The resulting AgCl cake was washed with deionized H2O
62.5 μmol, 5 mol-%) under argon atmosphere. The mixture was
stirred at r.t. for 24 h, TLC indicated the reaction was complete. The
solvent was removed under reduced pressure and the residue was
purified by flash chromatography on silica gel (petroleum ether/
(20 mL × 2). The filtrate was combined and concentrated in vacuo ethyl acetate = 10:1) to give 17[43] (380 mg, 69 % for 6e and 360 mg,
to afford a blue liquid, which was further dried under high vacuum
at 100 °C for 2 min to afford Cu(FSI)2·4H2O (7) as a blue crystal
(2.44 g, 98 %): 19F NMR (282 MHz, H2O) δ = 49.55; elemental analysis
calcd. (%) for CuF4HN2O8S4 H 0.24, N 6.59, found H 2.88, N 5.65.
64 % for 6e′) as a white solid: 1H NMR (500 MHz, CDCl3) δ = 7.63
(d, J = 7.9 Hz, 2H), 7.31–7.20 (m, 5H), 7.04–6.94 (m, 2H), 6.20 (s, 1H),
4.54 (s, 1H), 2.62 (s, 3H), 2.43 (s, 3H), 2.04 (s, 3H), 1.88–1.80 (m, 1H),
1.74–1.65 (m, 1H), 1.37–1.05 (m, 4H), 0.82 (t, J = 7.1 Hz, 3H).
Catalytic Applications – Reaction A: Gold(I)-catalyzed propargyl
Reaction E: Ir(III)-catalyzed C-H hydroarylation. To a mixture of
ester hydration. To a solution of 8 (220 mg, 1.26 mmol) in acetone 18 (310.4 mg, 2.00 mmol), 2 (0.270 mL, 2.40 mmol), [IrCp*Cl2]2
(12.5 mL, 0.1 M) were added Au(I) catalyst (8.1 mg 6a or 9.3 mg 6a′,
12.6 μmol, 1.0 mol-%) and H2O (67 μL, 3.7 mmol) at r.t. under argon
atmosphere. The reaction mixture was stirred at r.t. for 6 h, TLC
(80.0 mg, 0.10 mmol), Ag(I) complex (1, 2, 5, or AgNTf2, 0.40 mmol,
20 mol-%) in a 25 mL sealed Schlenk tube equipped with a Teflon
stirbar was added dry ClCH2CH2Cl (5.0 mL) under atmospheric con-
indicated the reaction was complete. The solvent was removed un- ditions. The tube was sealed and the reaction mixture was stirred
der reduced pressure and the residue was purified by flash chroma-
tography on silica gel (petroleum ether/ethyl acetate = 20:1 to
in a pre-heated oil bath at 120 °C for 6 h. The reaction was cooled
to room temperature, filtered through a plug of celite and then
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e) A. Bihlmeier, M. Gonsior, I. Raabe, N. Trapp, I. Krossing, Chem. Eur. J.
2004, 10, 5041–5051.
washed with ethyl acetate (20 mL × 3). The solvents were removed
under reduced pressure. The residue was purified by flash chroma-
tography on silica gel (petroleum ether/ethyl acetate = 6:1) to give
20[45] and 21 as yellow oil. The yields and ratios were shown in
Scheme 6. Data for 20: H NMR (300 MHz, CDCl3) δ = 8.77–8.56 (m,
1H), 7.76 (td, J = 7.7, 1.9 Hz, 1H), 7.55–7.13 (m, 6H), 4.06 (q, J =
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1
7.1 Hz, 2H), 3.05 (t, J = 8.0 Hz, 2H), 2.53 (dd, J = 8.8, 7.2 Hz, 2H),
1
1.19 (t, J = 7.2 Hz, 3H). Data for 21: H NMR (300 MHz, CDCl3) δ =
8.84–8.56 (m, 1H), 7.79 (td, J = 7.6, 1.9 Hz, 1H), 7.40–7.22 (m, 3H),
7.17–7.15 (m, 2H), 4.04 (q, J = 7.2 Hz, 4H), 2.65 (m, 4H), 2.41 (m, 4H),
1.18 (t, J = 7.1 Hz, 6H).
[4]
[5]
Reaction F: Cu(II)-catalyzed per-O-acetylation of glucose. To a
mixture of glucose 22 (1.80 g, 10 mmol) and Ac2O (5.20 mL,
55 mmol) was added complex 7 (50.0 mg, 0.10 mmol, 1.0 mol-%).
The mixture was stirred at r.t. for 14 hour, TLC indicated the reaction
was complete. The mixture was diluted with CH2Cl2 (50 mL) and
the mixture was washed with aqueous NaHCO3 followed by brine.
The organic phase was dried with anhydrous Na2SO4, and was then
filtered and concentrated in vacuo. The crude product was purified
by flash column chromatography (petroleum ether/ethyl acetate =
3:1) to afford product 23[46] as a white solid (3.72 g, 95 %, α/ꢀ =
3.2:1): 1H NMR (500 MHz, CDCl3) δ = 6.32 (d, J = 3.6 Hz, 1.00H), 5.71
(d, J = 8.3 Hz, 0.31H), 5.46 (t, J = 9.9 Hz, 1.05H), 5.28–5.21 (m, 0.39H),
5.17–5.04 (m, 2.62H), 4.32–4.22 (m, 1.40H), 4.15–4.04 (m, 2.53H), 3.83
(ddd, J = 10.1, 4.6, 2.2 Hz, 0.35H), 2.17 (s, 2.92H), 2.11 (s, 0.89H), 2.08
(s, 2.70H), 2.08 (s, 1.25H), 2.03 (s, 2.82H), 2.02 (s, 1.33H), 2.02 (s,
2.88H), 2.01 (s, 3.46H); 13C NMR (126 MHz, CDCl3) δ = 170.73, 170.70,
170.33, 170.20, 169.76, 169.50, 169.35, 169.06, 168.85, 91.83, 89.19,
72.92, 72.86, 70.36, 69.96, 69.32, 68.02, 67.88, 61.59, 21.00, 20.94,
20.82, 20.79, 20.69, 20.68, 20.57.
[6]
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Acknowledgments
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The current price of reagent grade (98 %) HOTf from Sigma-Aldrich is
$148/100 g, and HNTf2 (> 95.0 %) is $104/5g.
For recently developed weakly coordinating anions, see: a) I. M. Riddle-
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Financial support from the National Natural Science Foundation
of China (21432012 and 21621002), the Strategic Priority Re-
search Program of CAS (XDB20020000), the K. C. Wong Educa-
tion Foundation, the Shanghai Sailing Program (17YF1424000),
and the China Postdoctoral Science Foundation (2017LH038) is
acknowledged. We are grateful to Mr. Jie Sun and Xuebing Leng
for their help in X-ray diffraction analysis.
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Keywords: Coinage metals · Silver · Gold · Structure
elucidation · Homogeneous catalysis
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Received: September 30, 2019
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Full Paper
Coinage Metal Complexes
A series of silver(I), gold(I), and cop-
per(II) (bisfluorosulfonyl)imide (–FSI)
complexes are prepared from KFSI, an
inexpensive chemical, and shown in-
teresting structural features and some
unprecedented coordination modes.
They exhibit comparable catalytic per-
formance to the corresponding coin-
age metal triflimides (–NTf2) in a series
of the model chemical transforma-
tions.
Y. Tang, B. Yu* .................................. 1–13
Coinage Metal (Bisfluorosulfonyl)-
imide Complexes: Preparation, Char-
acterization, and Catalytic Applica-
tions
DOI: 10.1002/ejic.201901058
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim