Gold(I) Complexes of P,N ligands and their catalytic activity

Article abstract of DOI:10.1002/ejic.200900964

Gold(I) complexes were readily prepared by reaction of the respective ligands with (Me₂S)AuCl in CH₂Cl₂. Complexes of formula LAuCl (L = diphenyl(2-pyridyl)phosphane (PPh₂Py), (R)-(+)-4-[(2)-(dlphenylphosphanyl)-1-naphthyl]N-[(R)-1-phenyIethyl] -1-phthalazinamine (PINAP)) were obtained when a 1:1 molar ratio of ligand to starting gold precursor was used. When a 2:1 ratio of ligand to gold precursor was used with PPh₂Py or MandyPhos as ligands, complexes of the type L₂AuCl were obtained. All complexes were fully characterized, and single-crystal X-ray structures could be determined for four complexes. Chloride ions were removed by reaction with silver salts, such as AgNTf₂, AgOTf and AgBF₄, for the use of these complexes as catalysts. After the catalytic reaction with alkynes and alcohols in acetonitrile, a unique trinuclear gold(I) complex derived from [(PPh₂Py)-Au]BF₄ could be characterized by X-ray structural analysis, showing a mode of catalyst deactivation.

Full text of DOI:10.1002/ejic.200900964

FULL PAPER
DOI: 10.1002/ejic.200900964
Gold(I) Complexes of P,N Ligands and Their Catalytic Activity
Chosu Khin,[a] A. Stephen K. Hashmi,*[a,b] and Frank Rominger[b]
Keywords: Transition metals / Gold / Lewis acids / N ligands / P ligands / Cations
Gold(I) complexes were readily prepared by reaction of the
respective ligands with (Me2S)AuCl in CH2Cl2. Complexes
characterized, and single-crystal X-ray structures could be
determined for four complexes. Chloride ions were removed
by reaction with silver salts, such as AgNTf2, AgOTf and
AgBF4, for the use of these complexes as catalysts. After the
catalytic reaction with alkynes and alcohols in acetonitrile, a
unique trinuclear gold(I) complex derived from [(PPh2Py)-
Au]BF4 could be characterized by X-ray structural analysis,
showing a mode of catalyst deactivation.
of formula LAuCl {L
=
diphenyl(2-pyridyl)phosphane
(PPh2Py), (R)-(+)-4-[(2)-(diphenylphosphanyl)-1-naphthyl]-
N-[(R)-1-phenylethyl]-1-phthalazinamine (PINAP)} were ob-
tained when a 1:1 molar ratio of ligand to starting gold pre-
cursor was used. When a 2:1 ratio of ligand to gold precursor
was used with PPh2Py or MandyPhos as ligands, complexes
of the type L2AuCl were obtained. All complexes were fully
Introduction
The exponential expansion of research interest involving
gold in this decade has led to the discovery of many inter-
esting properties and applications of this precious metal.
The research on gold covers its various oxidation states
(mainly 0, +1, +3, and seldom +2), its coordination chemis-
try and complexes,[1] the photophysical[2] and catalytic[3]
properties of its complexes, and many other areas.[4]
The coordination chemistry of gold(I) complexes, in par-
ticular, is well-established. The most striking feature of this
d10 ion of the group 11 transition metal gold, AuI, is linear
dicoordinate complex formation, whereas CuI and AgI
commonly exist as tetracoordinate species. The favourable
linear coordination geometry of gold(I) complexes was as-
sumed to be based on the highest relativistic effect that gold
has along the periodic trend, leading to efficient overlap-
ping of s, p and d orbitals.[1c] Tri- and tetracoordinate
gold(I) complexes also exist, although they are less com-
mon. This may be due to the higher energy required for Au
than for Cu and Ag to go from planarity to more distorted
angles, as shown by DFT calculations.[5]
Figure 1. Phosphane ligands used for the synthesis of AuI com-
plexes.
Results and Discussion
In this paper we report the exploration of gold(I) com-
plexes of the P-sp2-N-ligands {diphenyl(2-pyridyl)phos-
phane (PPh2Py), (R)-(+)-4-[(2)-(diphenylphosphanyl)-1-
naphthyl]-N-[(R)-1-phenylethyl]-1-phthalazinamine (PINAP)
Simple treatment of a solution of ligand L (L = PPh2Py
or PINAP) with one molar equivalent of (Me2S)AuCl in
dichloromethane gives colourless to pale yellow solutions,
from which colourless crystals of [LAuCl] are obtained in
91 or 82% yield, respectively, after slow diffusion of hexane
vapour into the solution.
and
chiral
P-sp3-N-ferrocenyl-based
diphosphane
(MandyPhos)} (Figure 1) and their use as catalysts.
We investigated a single crystal of [(PPh2Py)AuCl] (1a):
in the structure determination a decent R value was ob-
tained, but that was dominated by the gold, and because of
the overall low quality of the crystal, the aromatic rings had
to be treated as fixed hexagons in order to refine them. This
[a] Catalysis Research Laboratory (CaRLa),
Im Neuenheimer Feld 584, 69120 Heidelberg Germany
[b] Organisch-Chemisches Institut, Universität Heidelberg,
Im Neuenheimer Feld 270, 69120 Heidelberg Germany
Fax: +49-6221-544205
E-mail: hashmi@hashmi.de
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C. Khin, A. S. K. Hashmi, F. Rominger
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did not allow to distinguish the benzene rings from the pyr- P(1) is 137.3(9)°. The P(2)–Au(1)–Cl(1) and P(1)–Au(1)–
idine ring, so overall one can only say that the structure is Cl(1) bond angles are 114.5(1) and 107.7(1)°, respectively.
quite similar to that of [Ph3PAuCl].[6] The structure of the These physical features of complex 2 lie midway between
dicoordinate gold(I) complex [(PINAP)AuCl] (1b), as deter- two other very similar structures made of phosphane li-
mined by an X-ray crystal structure analysis,[7] is shown in gands.[9a,9c] A summary of important interatomic distances
Figure 2. Complex 1b adopts a nearly linear geometry in and angles of these chloridobis(phosphanyl)gold(I) com-
which the gold atom is coordinated by the phosphorus plexes is given in Table 1.
atom of the phosphane ligand and the chlorido ligand. The
P–Au–Cl bond angle is 178.1(8)°. The two aromatic rings,
those of the naphthyl and the phthalazinyl groups, lie per-
pendicular to each other, and they are orthogonal to P–Au–
Cl axis. The Au–P and Au–Cl bond lengths of 1b are 2.23(6)
and 2.28(6) Å, respectively, which indicates no unusual
structural alteration from many gold(I) complexes known
in the literature.[8]
Table 1. Summary of important interatomic distances [Å] and
angles [°].
Compound
Au–X
Au–P(1)
Au–P(2)
P(1)–Au–P(2)
(Ph3P)2AuCl
(PhCy2P)2AuCl 2.744(2)
2.500(4)
2.323(4)
2.324(1)
2.339(4)
2.300(1)
132.1(1)
158.24(5)
The most intriguing aspect of 2 is the comparison of an-
gle P(2)–Au(1)–P(1) (Є PAuP) with that of similar com-
plexes. This angle lies closer to that of [(Ph3P)2AuCl], show-
ing a nearly trigonal planar geometry of the complex. The
slightly larger Є PAuP of 2 causes a tighter bonding be-
tween AuI and phosphorus atoms of the ligands. A slightly
longer Au–Cl bond was also observed for 2 relative to
[(Ph3P)2AuCl]. On the other hand, [(PhCy2P)2AuCl] shows
a distorted nature with a nearly linear arrangement between
the two phosphorus atoms and the gold atom (Є PAuP
158.2°). Nonetheless, the Au–P distances of [(PhCy2P)2-
AuCl] are comparable to 2, the most striking difference be-
ing observed in the Au–Cl distance [2.74(4) Å].
The approach to obtain 2 was also used to synthesize
tricoordinate gold(I) complexes containing a chiral phos-
phane ligand, specifically by using the MandyPhos ligand
(Figure 4). The resultant crystal was obtained as a tricoord-
inate polymer of formula [{(MandyPhos)AuCl}n] (3). Only
a few examples[11] exist in the literature for polymeric
gold(I) complexes, but compound 3 shown here is the first
evidence of a polymeric tricoordinate gold(I) complex con-
taining a chiral phosphane ligand.
The structure of 3 comprises a polymeric chain structure
involving bridging ferrocenylphosphane units linking trigo-
nal Au–Cl groups. Although a 1:1 molar ratio of ligand
to gold was observed, the two phosphorus atoms of one
MandyPhos ligand are coordinated to different AuI ions. In
other words, the MandyPhos ligand acts as a bridging li-
gand between two AuI ions. A similar polymeric structure
was obtained by Houlton et al. by using the diphosphane
ligand.[11c] Table 2 shows the selected bond lengths and
angles of complex 3 relative to the most structurally similar
complex, [{(µ-dppf)AuCl}n] [dppf = 1,1Ј-bis(diphenylphos-
phanyl)ferrocene].[11c] The most noticeable feature of the
two structures is that the P–Au–P angle is smaller for 3,
which is reflected in longer Au–P bond lengths.
Figure 2. Dicoordinate gold(I) complex [(PINAP)AuCl] (1b).
Addition of a twofold excess of ligand (L = PPh2Py)
solution to the (Me2S)gold(I) chloride in dichloromethane
produced a colourless solution, which was concentrated and
diffused with hexane. This afforded colourless crystals in
67% yield. The single-crystal X-ray structural analysis of
the crystal shows a less common tricoordinate gold(I) com-
plex, [(PPh2Py)2AuCl] (2) (Figure 3). Although a large fam-
ily of tricoordinate gold(I) complexes is known, there is
only a dozen crystal structures bearing two monodentate
phosphane ligands on the gold centre;[9] most of the other
known structures contain multidentate ligands or are even
substructures of multinuclear gold(I) complexes.[1,10]
Figure 3. Tricoordinate gold(I) complex [(PPh2Py)2AuCl] (2).
The Au–P bond lengths of 3 throughout the polymer
Compound 2 shows a trigonal planar geometry con- structure range from 2.329(5) to 2.347(5) Å. The slightly
sisting of one gold, two phosphorus and one chlorine longer Au–P bond lengths of 3 relative to Au–P bond
atoms. The two phosphane ligands coordinate to the AuI lengths of other gold(I) complexes could be rationalized as
centre with an Au(1)–P(1) distance of 2.32(2) Å and an by the explanation that the metallocene unit pulls the elec-
Au(1)–P(2) distance of 2.30(5) Å. The third coordination tron density away from phosphorus atom for better binding
site is occupied by a chlorido ligand with an Au(1)–Cl(1) with AuI. However, the Au–Cl bond lengths of 3 show no
bond length of 2.54(4) Å. The bond angle of P(2)–Au(1)– significant variation.
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Eur. J. Inorg. Chem. 2010, 1063–1069

Gold(I) Complexes of P,N Ligands and Their Catalytic Activity
Figure 4. Tricoordinate gold(I) complex [{(MandyPhos)AuCl}n] (3).
Table 2. Selected bond lengths [Å] and angles [°] of 3.
Table 3. Catalyzed addition of water to 1-pentyne in acetonitrile,
delivering 2-pentanone.
[{(MandyPhos)AuCl}n]
[{(µ-dppf)AuCl}n]
Entry
Catalyst
Amount [mol-%] T [°C] % Yield[a]
Au(1)–P(1)
Au(1)–P(2)
2.336(5)
2.343(5)
2.315(2)
1
2
3
4
5
6
7
8
9
10
[AuPPh2Py]NTf2
[AuPPh2Py]OTf
[AuPPh2Py]OTf
[AuPPh2Py]OTf
[AuPPh2Py]OTf
[AuPPh2Py]BF4
[AuPPh2Py]BF4
[AuPPh2Py]BF4
[AuPPh2Py]BF4
[AuPPh2Py]BF4
5
5
3
2
1
5
3
2
1
50
70
70
70
70
50
50
70
50
50
100
100
67
65
61
100
85
55
40
23
Au(1)–Cl(1)
Au(2)–P(4)
2.572(6)
2.329(5)
2.550(3)
Au(2)–P(3)
Au(2)–Cl(2)
2.347(5)
2.590(6)
P(1)–Au(1)–P(2)
P(1)–Au(1)–Cl(1)
P(2)–Au(1)–Cl(1)
P(4)–Au(1)–P(3)
P(4)–Au(2)–Cl(2)
P(3)–Au(2)–Cl(2)
133.01(19)
116.00(18)
110.98(18)
138.0(2)
113.77(18)
108.22(19)
136.5(1)
112.7(1)
110.8(1)
0.5
[a] Against an internal standard of the nonvolatile tert-butylacet-
amide.
When an equimolar amount of a silver salt of various
Fortunately, the unprecedented outcome of one of the
–
–
anions, BF4 , OTf– and NTf2 , was added to a solution con- catalytic reactions is the insight on how the activated
taining gold(I) complexes in dichloromethane, immediate gold(I) catalyst with the PPh2Py ligand became inactive
precipitation of AgCl was observed. The solution was fil- during the reaction. On one hand, a gold mirror deposited
tered, and the solvent was removed. The attempts to crys- onto the glass surface was observed in many of the reac-
tallize the complex after chloride ion removal only resulted tions run with [(PPh2Py)Au]BF4 as catalyst. On the other
in oily material.
hand, in some cases, red crystalline material aggregated on
Having prepared these nearly linear and distorted trigo- the glass surface after the reaction. Single-crystal X-ray
nal planar tricoordinate chloridogold(I) complexes and hav- structural analysis of the deposited crystal on the glass
ing removed the chloride ions from these complexes, we shows formation of the unique trinuclear gold(I) aggregate
tested them for the simple gold-catalyzed addition of water 4, which is the deactivated catalyst (Figure 5).
–
to 1-pentyne. This addition follows the normal Markovni-
Structure 4 crystallizes as a unit cell with three BF4
kov regioselectivity, and the only product observed is 2- counterions statistically distributed over four sites in the lat-
–
pentanone (Table 3). The NTf2 salt derived from 1a leads tice. Each Au(1), Au(2) and Au(3) atom of the cluster is still
to a good conversion to the product at 50 °C (entry 1). The coordinated to the P atom of the initial PPh2Py ligand. The
corresponding triflate needs 70 °C to reach completion (en- Au–P distances are 2.238(2), 2.237(2) and 2.239(2) Å for
try 2), reducing the amount of catalyst also reduces the Au(1), Au(2) and Au(3), respectively. These bond lengths
–
yield (entries 3–5), no full conversion is observed. The BF4
are slightly longer than those in 1a. Each Au atom is also
salt operates at 50 °C, again the yield drops significantly coordinated to the nitrogen atom of the pyridine group of
with the catalyst amount (entries 6–10). Overall, the turn- the PPh2Py ligand of the adjacent gold complex, thus com-
over numbers are in no way outstanding (between 5 and pleting the homonuclear gold complex. The Au–N dis-
20),[3] but they raise the interesting question of the modes tances are measured to be 2.100(7), 2.103(8) and 2.115(8) Å
of catalyst deactivation.
for Au(1)–N(3), Au(2)–N(1) and Au(3)–N(2), respectively.
Eur. J. Inorg. Chem. 2010, 1063–1069
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C. Khin, A. S. K. Hashmi, F. Rominger
FULL PAPER
by forming unique gold aggregates. Photophysical proper-
ties of these complexes may be one interesting aspect for
future study.
Experimental Section
General: All procedures were carried out under a dry argon atmo-
sphere using Schlenk and vacuum-line techniques. All solvents were
dried and purified by an MBRAUN Solvents Purification System
(SPS-800). All common reagents were used as purchased without
further purification. The starting gold complex, [(Me2S)AuCl], was
obtained from Aldrich Chemicals and used as received.
All NMR spectra were recorded with a Bruker Avance 200
(200.2 MHz for 1H, 50.3 MHz for 13C, and 80.02 MHz for 31P
NMR spectra) instrument. 1H and 13C NMR chemical shifts are
Figure 5. Deactivated gold(I) trimer observed after a catalytic reac-
tion (4).
1
reported in ppm relative to the H and 13C residues of the deuter-
ated solvents. 31P NMR chemical shifts are reported in ppm relative
to an 85% H3PO4 external standard solution. ESI mass spectra
were recorded with a Finnigan TSQ700 Tripelquadrupole mass
spectrometer. Gas chromatography–mass spectrometry (GC–MS)
was performed with an Agilent 6890N gas chromatograph fitted
with a 7683B Series mass selective detector.
These bond lengths are comparable to other known Au–N
distances.[12] The Au(2) atom of the cluster formed a tetra-
coordinate center, coordinating to Au(1) and Au(3) in ad-
dition to Au–P and Au–N bonding. The Au(2)–Au(1) and
Au(2)–Au(3) bond lengths are measured to be 3.048(3) and
3.226(9) Å, respectively. Once again, these bond lengths lie
within the range that was observed in the literature.[13] It
appeared that [(PPh2Py)Au]+ in the reaction solution be-
comes deactivated by coordinating with the nitrogen atom
of the ligand of the adjacent complex. Table 4 lists the high-
lighted parameters (bond lengths [Å] and bond angles [°])
of the crystal.
X-ray Structural Determinations: Frames corresponding to a sphere
of data were collected by using 0.3° ω scans with a SMART CCD
area detector: Mo-Kα, λ = 0.71073 Å radiation. Intensities were
corrected for Lorentz and polarization effects, and an empirical
absorption correction was applied by using the SADABS[14] pro-
gram based on the Laue symmetry of the reciprocal space. Struc-
ture solution and refinement was carried out with the SHELXL-
97[14] program system.
General Procedure for the Synthesis of Gold(I) Chloride Complexes:
All procedures were carried out under an argon atmosphere. To a
stirred solution of [(Me2S)AuCl] was added by cannula in the dark
the ligand solution in CH2Cl2. The reaction solution was stirred
for at least 2 h at room temperature. The resulting solution was
then concentrated under vacuum, and hexane was layered on the
concentrated solution to precipitate white powders. The product
precipitate was filtered and recrystallized with CH2Cl2/hexane.
Table 4. Selected bond lengths [Å] and bond angles [°] of 4.
[(PPh2Py)3Au3]3+
Au(1)–N(3)
Au(1)–P(1)
Au(1)–Au(2)
Au(1)–Au(3)
Au(2)–N(1)
Au(2)–P(2)
Au(3)–N(2)
Au(3)–P(3)
2.100(7)
2.238(2)
3.0483(6)
3.2269(7)
2.103(8)
2.237(2)
2.115(8)
2.239(2)
[Diphenyl(2-pyridyl)phosphane]gold(I) Chloride [(PPh2Py)AuCl]
(1a):
A solution of diphenyl(2-pyridyl)phosphane (489 mg,
1.90 mmol) in CH2Cl2 (50 mL) was added to a stirred solution of
[(Me2S)AuCl] (547 mg, 1.90 mmol) in CH2Cl2 (50 mL) at room
temperature under argon. The mixture was stirred for 2 h, then it
was concentrated under reduced pressure, and hexane was added
to precipitate out the product as a white powder; yield 867 mg,
92%. 1H NMR (200.2 MHz, CD2Cl2, 298 K): δ = 7.2–7.9 (m, 13
H, Ph, Py), 8.75 [d, J(H,H) = 4.6 Hz, 1 H, Py] ppm. 13C NMR
(50.3 MHz, CD2Cl2, 298 K): δ = 125.9 (1 C), 128.3 (1 C), 129.4 (4
C), 131.3 (1 C), 132.2 (1 C), 132.4 (2 C), 134.9 (4 C), 137.1 (2 C),
151.7 (1 C) ppm. 31P NMR (81.02 MHz, CD2Cl2, 298 K): δ = 32.4
N(3)–Au(1)–P(1)
N(3)–Au(1)–Au(2)
P(1)–Au(1)–Au(2)
N(3)–Au(1)–Au(3)
P(1)–Au(1)–Au(3)
Au(2)–Au(1)–Au(3)
N(1)–Au(2)–P(2)
N(1)–Au(2)–Au(1)
P(2)–Au(2)–Au(1)
N(2)–Au(3)–P(3)
N(2)–Au(3)–Au(1)
P(3)–Au(3)–Au(1)
168.3(2)
111.8(2)
75.91(7)
80.3(2)
110.29(7)
80.478(14)
171.9(2)
82.3(2)
105.69(7)
175.3(2)
114.3(2)
68.81(6)
(s) ppm. FAB+: calcd. m/z
=
460 for [(PPh2Py)Au]+
(C17H14AuNP); found m/z (%) = 460 (100). C17H14AuClP (495.69):
calcd. C 41.19, H 2.85, N 2.83; found C 40.57, H 2.86, N 2.76. IR
(KBr): ν = 513 (s), 545 (s), 692 (s), 727 (m), 749 (s), 770 (m), 988
˜
(m), 998 (w), 1102 (s), 1183 (w), 1422 (m), 1436 (s), 1449 (w), 1480
Conclusions
(m), 1571 (m), 1628 (m), 3052 (m) cm–1.
We have synthesized and characterized an array of
gold(I) complexes that contain strikingly different struc-
tural properties. Some of the complexes shown here have
{(R)-(+)-4-[2-(Diphenylphosphanyl)-1-naphthyl]-N-[(R)-1-phenyl-
ethyl]-1-phthalazinamine}gold(I) Chloride [(PINAP)AuCl] (1b): To a
stirred solution of [(Me2S)AuCl] (39.3 mg, 133 µmol) in CH2Cl2
catalytic activities, which, for example, become deactivated (20 mL) was added a solution of (R)-(+)-4-[2-(diphenylphos-
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Gold(I) Complexes of P,N Ligands and Their Catalytic Activity
phanyl)-1-naphthalenyl]-N-[(R)-1-phenylethyl]-1-phthalazinamine
cient:
5.136 mm–1,
F(000)
=
744,
crystal
size:
(74.7 mg, 134 µmol) in CH2Cl2 (20 mL) at room temperature under 0.31ϫ0.05ϫ0.01 mm, θ range for data collection: 1.61–24.71°, li-
1
argon. Work-up as described for 1a; yield 85.9 mg, 82%. H NMR
(200.2 MHz, CD2Cl2, 298 K): δ = 1.65 [d, J(H,H) = 6.5 Hz, 3 H,
miting indices: –12/12, –13/13, –16/16, 11994 reflections collected:
5095 unique [R(int) = 0.0469], completeness to θ = 24.71:99.7%,
CH3], 5.45 (m, 1H NH), 5.87 (m, 1 H, CH), 6.90–7.90 (m, 25 H, absorption correction: semiempirical from equivalents, max./min.
phenyl, phthalizine and naphthalene groups) ppm. 13C NMR
transmission: +0.9504 and 0.2989, refinement method: full-matrix
(50.3 MHz, CD2Cl2, 298 K): δ = 22.7 (CH3), 51.1 (CH), 118.0 (C), least-squares on F2, data/restraints/parameters: 5095/0/361, good-
120.9 (CH), 126.9 (CH), 127.9 (CH), 127.3 (CH), 127.5 (CH), 128.4 ness of fit on F2 = 1.021, final R indices [I Ͼ 2σ(I)]: R1 = 0.0456,
(CH), 128.5 (CH), 128. 6 (CH), 128.6 (CH), 128.63 (CH), 128.7 wR2 = 0.0974, R indices (all data): R1 = 0.0552, wR2 = 0.1012,
(CH), 128.7 (CH), 129.0 (CH), 130.1 (CH), 131.3 (CH), 131.4
(CH), 133.5 (two separate signals, CH), 133.6 (C), 133.7 (CH),
133.9 (CH), 134.0 (C), 134.1 (CH), 136.3 (C), 136.6 (C), 137.4 (C),
137.6 (C), 137.9 (C), 138.2 (C), 141.9 (C), 142.5 (C), 145.0 (C),
152.8 (C), 152.9 (C), 153.0 (C) ppm. 31P NMR (81.0 MHz, CD2Cl2,
298 K): δ = 28.72 (s) ppm. MS (ESI+): calcd. for [AuLCl + H]+
(C38H31AuClN3P) 792.153; found 792.1605. C38H30AuClN3P
(792.06): calcd. C 57.70, H 3.67, N 5.31; found C 58.62, H 4.23, N
largest diff. peak and hole: 1.272 and –1.953 eA–3.
(MandyPhos)gold(I) Chloride [{(MandyPhos)AuCl}n] (3): To
a
stirred solution of [(Me2S)AuCl] (3.00 mg, 10.0 µmol) in CH2Cl2
(1.0 mL) was added a solution of MandyPhos (16.0 mg, 20.0 µmol)
in CH2Cl2 (1.0 mL) at room temperature under argon. Work-up as
described for 1a; yield 10.9 mg (61%). 1H NMR (200.2 MHz,
CD2Cl2, 298 K): δ = 1.30 (s, 12 H, NCH3), 3.21 (br. s, 2 H, NCH),
3.52 (br. s, 2 H, CH), 4.48 (br. s, 2 H, ferrocene), 4.59 (br. s, 2 H,
ferrocene), 6.90–7.25 (m, 30 H, Ph) ppm. 13C NMR (50.3 MHz,
CD2Cl2, 298 K): δ = 40.5 (4 C, CH3), 67.4 (2 C), 71.2 (2 C, Cp),
72.5 (2 C, Cp) 73.3 (2 C, Cp), 74.9 (2 C, Cp), 96.9 (2 C, Cp), 126.1
(2 C, Ph), 126.8 (2 C, Ph), 127.2 (2 C, Ph), 127.4 (4 C, Ph) 128.1
(12 C, Ph), 128.5 (2 C, Ph), 129.1 (4 C, Ph) 131.7 (2 C, Ph), 134.0 (2
C, Ph), 135.9 (2 C, Ph), 137.7 (2 C, Ph) ppm. 31P NMR (81.0 MHz,
CD2Cl2, 298 K): δ = –9.69 to –11.31 (broad) ppm. MS (ESI+):
5.24. IR (KBr): ν = 505 (w), 520 (w), 540 (m), 664 (w), 693 (s), 749
˜
(m), 1099 (m), 1129 (w), 1365 (m), 1394 (w), 1437 (s), 1485 (m),
1507 (s), 1551 (w), 1579 (w), 1629 (m, broad), 2923 (m), 3057 (w)
cm–1.
Single-Crystal X-ray Structure Determination for 1b: Empirical for-
mula: C40H34AuCl5N3P, formula weight: 961.89 gmol–1, T =
200(2) K, λ = 0.71073 Å, crystal system: monoclinic, space group:
P21, Z = 2, unit cell dimensions: a = 10.6441(1) Å; α = 90°; b =
9.2667(2) Å; β = 97.551(1)°; c = 19.3538(1) Å; γ = 90°; V =
1892.42(5) Å3; d(calculated) = 1.69 g/cm3; absorption coefficient:
calcd.
for
[AuL]+
1017.26207;
found
1017.25054.
C52H50AuClFeN2P2 (1053.18): calcd. C 59.14, H 4.9, N 2.65; found
C 59.93, H 4.96, N 2.62.
4.32 mm–1,
crystal
shape:
platelet,
crystal
size:
0.46ϫ0.12ϫ0.04 mm3, crystal colour: colourless, θ range for data
collection: 1.9 to 24.1°, limiting indices: –12Ͻ h Ͻ 12, –10 Ͻ k Ͻ
10, –22 Ͻ l Ͻ 22; reflections collected: 14205, independent reflec-
tions: 5935 [R(int) = 0.0925], observed reflections: 4480 [I Ͼ 2σ(I)],
absorption correction: semiempirical from equivalents, max./min.
transmission: 0.85/0.24, refinement method: full-matrix least-
squares on F2, data/restraints/parameters: 5935/8/238, goodness-of-
fit on F2 = 1.05, final R indices [I Ͼ 2σ(I)] = R1 = 0.075, wR2 =
0.159; absolute structure parameter: 0.066(17), largest diff. peak
and hole: 3.16 and –2.27 eÅ–3.
Single-Crystal X-ray Structure Determination for 3: Empirical for-
mula: C52.50H51AuCl2FeN2P2; formula weight: 1095.61 gmol–1, T
= 200(2) K, λ = 0.71073 Å, crystal system: orthorhombic, space
group: P2(1)2(1)2(1), unit cell dimensions: a = 14.5722(3) Å; α =
90°, b = 35.3453(8) Å; β = 90°, c = 22.9088(5) Å; γ = 90°, V =
11799.4(4) A3, Z = 8, calculated density: 1.233 Mg/m3, absorption
coefficient: 2.905 mm–1, F(000)
=
4392, crystal size:
0.36ϫ0.33ϫ0.24 mm, θ range for data collection: 1.06 to 25.71°,
limiting indices: –17 Յ h Յ 17, –42 Յ k Յ 43, –27 Յ l Յ 27,
reflections collected/unique: 97175/22432 [R(int) = 0.1365], com-
pleteness to θ = 25.71 (99.9%), absorption correction: semiempir-
ical from equivalents, max./min. transmission: 0.5424 and 0.4211,
refinement method: full-matrix least-squares on F2, data/restraints/
parameters: 22432/0/1063, goodness-of-fit on F2 = 1.081, final R
indices [I Ͼ 2σ(I)]: R1 = 0.1017, wR2 = 0.2671, R indices (all data):
Bis[diphenyl(2-pyridyl)phosphane]gold(I) Chloride [(PPh2Py)2AuCl]
(2): To a stirred solution of (Me2S)AuCl (59.0 mg, 20.0 mmol) in
CH2Cl2 (10 mL) was added a solution of diphenyl(2-pyridyl)phos-
phane (105 mg, 40.0 mmol) in CH2Cl2 (10 mL) at room tempera-
ture under argon. The solution mixture was stirred for 2 h. The
solution was concentrated under reduced pressure, and hexane was
added to precipitate the product out as a white powder; yield
102 mg, 67%. 1H NMR (200.2 MHz, CD2Cl2, 298 K): δ = 7.15–
7.70 (m, 26 H, Ph, Py), 8.65 [d, J(C,H1) = 4.6 Hz, 2 H, Py] ppm.
13C NMR (50.3 MHz, CD2Cl2, 298 K): δ = 124.7 (2 C), 129.1 (8
C), 129.3 (2 C), 130.4 (2 C), 131.2 (4 C), 134.5 (8 C), 134.9 (2 C),
136.7 (2 C), 151.0 (2 C) ppm. 31P NMR (81.0 MHz, CD2Cl2,
298 K): δ = 27.98 (s) ppm. MS (ESI+): calcd. for [Au(PPh2Py)2]+
(C34H28AuN2P2) 723.1374 ; found 723.1374. C34H28AuClN2P2
(758.97): calcd. C 53.81, H 3.72, N 3.69; found C 53.41, H 3.68, N
R1
= 0.1564, wR2 = 0.3215, absolute structure parameter:
0.881(14), largest diff. peak and hole: 4.549 and –3.643 eA–3.
General Procedure for Chloride Ion Removal from (L)nAuCl Com-
plexes by Using Silver(I) Salts: To a stirred solution of [LAuCl] in
CH2Cl2 was added an equimolar amount of silver salt bearing
–
–
weakly coordinating counter anions, such as BF4 , OTf– and NTf2 .
Immediate precipitation of AgCl was observed in all cases. The
solution was stirred for 1 h, filtered, and the filtrate was concen-
trated to dryness. The resulting solid ranged in colour from greyish
white to purplish red.
3.65. IR (KBr): ν = 518 (s), 544 (w), 618 (w), 694 (s), 725 (w), 744
˜
Chloride Ion Removal from [(PPh2Py)AuCl] by Using AgNTf2: Re-
moval of Cl– resulted in a white precipitate in quantitative yield.
1H NMR (200.15 MHz, CD2Cl2, 298 K): δ = 7.22–7.61 (m, 11 H
ppm. Ph, Py), 7.89 (br. s, 1 H, Py), 8.09 [t, J(H,H) = 8.0 Hz, 1 H,
(s), 770 (w), 988 (w), 1027 (w), 1098 (m), 1156 (w), 1185 (w), 1422
(s), 1435 (m), 1449 (m), 1571 (s), 1631 (broad s), 3050 (m) cm–1.
Single-Crystal X-ray Structure Determination for 2: Empirical for-
mula: C34H28AuClN2P2, formula weight 758.95 gmol–1, colourless, Py], 9.08 [d, J(H,H) = 4.5 Hz, 1 H, Py]. 31P NMR (81.02 MHz,
T = 200 K, λ = 0.71073 Å, crystal system: triclinic, space group:
P1, unit cell dimensions: a = 10.7531 (13) Å; α = 113.516(3)°; b =
CD CN, 298 K): δ = 30.4 (s, PPh) ppm. IR (KBr): ν = 512 (s), 542
(s), 571 (s), 600 (s), 653 (m), 692 (s), 742 (m), 792 (w), 997 (w),
˜
3
¯
11.6519(14) Å; β = 94.768(3)°; c = 14.2282(18); γ = 109.098(3)°; V 1029 (m), 1058 (s), 1101 (m), 1140 (s), 1197 (s), 1350 (s), 1438 (m),
= 1497.0(3) A3; calculated density: 1.684 Mg/m3, absorption coeffi- 1592 (w), 1624 (w) cm–1.
Eur. J. Inorg. Chem. 2010, 1063–1069
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1067

C. Khin, A. S. K. Hashmi, F. Rominger
FULL PAPER
Chloride Ion Removal from [(PPh2Py)AuCl] by Using AgOTf: 1H
12.883(2) Å, β = 90.277(3)°, c = 24.540(4) Å, γ = 109.837(2)°, V =
NMR (200.15 MHz, CD2Cl2, 298 K): δ = 7.15 (m, 1 H, Py), 7.25– 3151.9(9) A3, Z = 2, calculated density: 1.864 Mg/m3, absorption
7.60 (m, 10 H, Ph, Py), 8.03 (m, 1 H, Py), 8.23 (m, 1 H, Py), 9.22
coefficient: 7.126 mm–1, F(000)
=
1674, crystal size:
[d, J(H,H) = 4.8 Hz, 1 H, Py] ppm. 31P NMR (81.02 MHz, 0.22ϫ0.14ϫ0.14 mm, θ range for data collection: 0.84 to 28.40°,
CD CN, 298 K): δ = 29.9 (s, PPh) ppm. IR (KBr): ν = 513 (s), 543
limiting indices: –14 Յ h Յ 14, –17 Յ k Յ 17, –32 Յ l Յ 32,
reflections collected/unique: 32034/15485 [R(int) = 0.0717], com-
pleteness to θ = 28.40 97.8%, absorption correction: semiempirical
from equivalents, max. and min. transmission: 0.4353 and 0.3032,
refinement method: full-matrix least-squares on F2, data/restraints/
parameters: 15485/0/749, goodness-of-fit on F2 = 1.004, final R in-
dices [I Ͼ 2σ(I)] R1 = 0.0564, wR2 = 0.1413, R indices (all data):
R1 = 0.0918; wR2 = 0.1617, largest diff. peak and hole: 2.073 and
–1.747 eA–3.
˜
3
(s), 573 (s), 638 (s), 693 (s), 714 (s), 727 (m), 752 (s), 997 (w), 1031
(s), 1101 (s), 1161 (s), 1260 (s), 1424 (w), 1437 (s), 1481 (w), 1572
(w), 1591 (w), 1625 (w) cm–1.
Chloride Ion Removal from [(PPh2Py)AuCl] by Using AgBF4: 1H
NMR (200.2 MHz, CD2Cl2, 298 K): δ = 7.18–7.67 (m, 13 H, Ph,
Py), 8.71 [d, J(H,H) = 5.3 Hz, 1 H, Py] ppm. 13C NMR (50.3 MHz,
CD2Cl2, 298 K): δ = 123.4 (1 C), 124.9 (1 C), 128.8 (1 C), 130.5 (4
C), 133.0 (2 C), 134.6 (2 C), 135.1 (4 C), 142.5 (1 C), 155.8 (1 C)
ppm. 31P NMR (81.02 MHz, CD2Cl2, 298 K): δ = 30.1 (s, PPh)
ppm. C17H14AuBF4NP (547.04): calcd. C 37.32, H 2.58, N 2.56;
Standard Procedure for AuI-Catalyzed Addition of Water: All ex-
periments were performed by using 5 mol-%, with regard to pen-
–
tyne, activated AuI complex of various counterions such as BF4 ,
found C 36.94, H 2.80, N 2.58. IR (KBr): ν = 501 (m), 512 (m),
˜
OTf– and NTf2 . The degassed and argon-purged pentyne, water
–
543 (s), 692 (m), 714 (m), 727 (w), 750 (m), 997 (m), 1101 (s), 1123
(s), 1185 (w), 1423 (w), 1427 (s), 1481 (w), 1571 (w), 1591 (w), 1628
(w), 3056 (w) cm–1.
(10 equiv.) and tert-butylacetamide as an internal standard were
added to sealed NMR tubes with a disposable syringe under an
argon atmosphere. A small amount (100 µL) of deuterated acetoni-
trile was added to the solution, and the proton NMR spectrum
at room temperature was measured as the initial spectrum of the
experiment. A catalytic amount of activated AuI complex dissolved
in a small amount of deuterated acetonitrile was then added to the
solution. The NMR solution tube was submerged in an oil bath
preheated to 50 °C, and the solution progress was monitored every
hour by NMR spectroscopy until no changes were observed after
48 h.
1
Chloride Ion Removal from [(PPh2Py)2AuCl] by Using AgNTf2: H
NMR (200.2 MHz, CD2Cl2, 298 K): δ = 7.25–7.65 (m, 24 H, Ph),
7.84 (m, 2 H, Py), 8.79 [d, J(H,H) = 4.0 Hz, 2 H, Py] ppm. 13C
NMR (50.3 MHz, CD2Cl2, 298 K): δ = 122.1 (2 C), 123.4 (2 C),
126.5 (2 C), 130.2 (8 C), 132.7 (4 C), 133.3 (4 C), 134.7 (8 C), 141.3
(2 C), 152.0 (2 C) ppm. 31P NMR (81.02 MHz, CD2Cl2, 298 K): δ
= 44.2 (s, PPh) ppm. MS (ESI+): calcd. for [Au(PPh2Py)2]+
(C H AuN P ) 723.139; found 723.1374. IR (KBr): ν = 512 (s),
˜
34 28
2 2
542 (s), 571 (s), 600 (s), 653 (m), 692 (s), 742 (m), 792 (w), 997 (w),
1029 (m), 1058 (s), 1101 (m), 1140 (s), 1197 (s), 1350 (s), 1438 (m),
1592 (w), 1624 (w) cm–1.
Product solutions at room temperature were filtered to remove de-
activated gold catalyst precipitates prior to the analysis. Product
solution (100 µL) diluted in acetonitrile was used for the analysis.
Percentage yields were calculated on the basis of the internal stan-
dard concentration.
Chloride Ion Removal from [(PINAP)AuCl] by Using AgBF4: Re-
moval of Cl– resulted in a white precipitate; yield 81.6%. 1H NMR
(200.2 MHz, CD2Cl2, 298 K): δ = 1.70 [d, J(H,H) = 6.8 Hz, 3 H],
6.16 (m, 2 H), 6.60–8.20 (m, phenyl, phthalizine and naphthalene
groups) ppm. 13C NMR (50.3 MHz, CD2Cl2, 298 K): δ = 20.2
(CH3), 50.0 (CH), 117.8 (C), 120.5 (CH), 126.1 (CH), 127.2 (CH),
126.9 (CH), 127.0 (CH), 127.7 (two separate signals), 127.9 (two
separate signals, CH), 128.0 (CH), 128.1 (two separate signals,
CH), 128.5 (CH), 129.9 (CH), 130.3 (CH), 130.4 (two separate sig-
nals, CH), 132.8 (CH), 132.5 (C), 132.7 (CH), 132.9 (CH), 133.6
(C), 133.9 (CH), 135.1 (C), 135.2 (C), 136.7 (C), 136.8 (C), 137.3
(C), 137.9 (C), 141.1 (C), 141.7 (C), 144.2 (C), 150.9 (C), 151.1 (C),
152.3 (C) ppm. 31P NMR (81.02 MHz, CD3CN, 298 K): δ = 30.61
Vacuum fractional distillation with Kugelrohr apparatus was per-
formed to isolate the products of the reaction. In general, a small
round-bottomed flask containing the product solution was slowly
heated under partial vacuum to fractionally collect the products
with different boiling points. The isolated products were further
analyzed by proton and carbon NMR spectroscopy.
Acknowledgments
(s) ppm. IR (KBr): ν = 505 (w), 519 (w), 535 (w), 665 (w), 693 (s),
˜
We are grateful for CaRLa of Heidelberg University being co-fi-
nanced by Heidelberg University, the State of Baden-Württemberg
and BASF SE.
750 (m), 998 (w), 1084 (s), 1124 (s), 1373 (w), 1395 (w), 1437 (s),
1508 (s), 1559 (w), 1581 (w), 3386–3588 (m, broad) cm–1.
[Diphenyl(2-pyridyl)phosphane]gold(I) Trimer (4): The gold(I) tri-
mer was collected as deactivated catalyst upon an attempted ad-
dition of tert-butyl alcohol to pentyne. A catalytic amount (5 mol-
%) of [biphenyl(2-pyridyl)phosphane]gold(I) tetrafluoroborate was
dissolved in a small amount of deuterated acetonitrile and added
to the bulk solution mixture in a J. Young NMR tube containing
the substrates tert-butyl alcohol and 1-pentyne under argon. The
reaction was carried out at 50 °C and followed by periodical proton
NMR spectroscopic measurements. Small crystals formed in the
NMR tube, which were analyzed by single-crystal X-ray diffrac-
tion. C53H45Au3B4F16N4P3 (1768.98): calcd. C 37.32, H 2.58, N
2.56; found C 37.02, H 2.66, N 2.61.
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 1063–1069

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[7] CCDC-748461 (for 1b), -748462 (for 2), -748463 (for 3) and
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from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
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Received: September 28, 2009
Published Online: January 26, 2010
Eur. J. Inorg. Chem. 2010, 1063–1069
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1069