Keto-stabilized Arsenic Ylides and their Coordination to Gold(I)

Article abstract of DOI:10.1002/zaac.202000110

Three different arsonium salts were prepared by a solvent-free method from Ph₃As and the respective 2-bromoacetophenones. These salts were deprotonated by NaOH to form keto-stabilized arsenic ylides. The ylids react with [AuCl(tht)] affording gold(I) complexes containing the C-bound ylide. The compounds were characterized by NMR spectroscopy, IR spectroscopy, and X-ray diffraction.

Full text of DOI:10.1002/zaac.202000110

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.202000110
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Keto-stabilized Arsenic Ylides and their Coordination to Gold(I)
Ferdinand Ehlers,[a] Jana M. Strumberger,[a] and Fabian Mohr*[a]
Herrn Professor Dr. Manfred Scheer zum 65. Geburtstag gewidmet.
Abstract. Three different arsonium salts were prepared by a solvent- nic ylides. The ylids react with [AuCl(tht)] affording gold(I) com-
free method from Ph3As and the respective 2-bromoacetophenones.
These salts were deprotonated by NaOH to form keto-stabilized arse-
plexes containing the C-bound ylide. The compounds were charac-
terized by NMR spectroscopy, IR spectroscopy, and X-ray diffraction.
Introduction
Burmeister showed that keto-stabilized phosphorus ylides co-
ordinated to PdII readily undergo orthometallation at either a
phenyl ring of the Ph3P moiety or the phenyl ring adjacent
to the carbonyl group.[7] In case of their arsenic counterparts,
orthometallation was only observed with MeC(O)CHAsPh3
but not with PhC(O)CHAsPh3.[7] Around the same time
Keto-stabilized phosphorus-derived ylides of the type
Ph3PCHC(O)R are a well-studied class of compounds, exhibit-
ing both diverse organic reactivity as well as rich coordination
chemistry with a variety of metals.[1] In contrast, not much is
known about the metal chemistry of the corresponding keto-
stabilized arsenic-ylides Ph3AsCHC(O)R, despite the fact that
the ylides themselves are quite old compounds. The formation
of arsonium salts from the reaction of triphenylarsine with
chloroacetone or 2-bromoacetophenone and their subsequent
deprotonation was first reported by Michaelis in two papers
from 1899 and 1902.[2] More than half a century later Nesmey-
anov and Frøyen independently studied the reactivity as well
Tanaka reported
a detailed NMR spectroscopic study
of some PtII and PdII-phosphine complexes of the type
[MX2(PR3)(ylide)] [M = Pd, Pd; X = Cl, Br, I; PR3 = PPhMe2,
PMe3] with various keto-stabilized phosphorus-, arsenic- and
sulfur-ylides.[8] Platinum(II) ethylene complexes containing C-
bound keto-stabilized phosphorus- and arsenic ylides of the
type trans-[PtCl2(η2-C2H4)(ylide)] are accessible from the re-
action of the respective ylides with K[PtCl3(η2-C2H4)].[9]
as physical and spectroscopic properties of these stabilized ar- There is also a more recent publication on palladium com-
senic ylides in more detail.[3] It was also Nesmeyanov who
showed that Ph3AsCHC(O)Ph formed a stable salt with HgCl2,
which was formulated as [HgCl{Ph3AsCHC(O)Ph}]Cl.[4]
Later, Buckle and Harrison reported that keto-stabilized As-
ylids act as C-bound ligands in a family of organotin(IV) com-
plexes. Their assignment was based on the IR-stretching fre-
quency of the carbonyl group.[5]
Palladium(II) and platinum(II) complexes of the type
[MCl2(ylide)2], prepared by two different methods, were re-
ported by the groups of Burmeister and Bravo in the mid-
1970’s. Based on IR- and NMR spectroscopy, the ylids were
assigned to bind to the metal through the carbon atom.[6]
Furthermore, Bravo observed a mixture of two stereoisomers
in solution by NMR spectroscopy, resulting from the chirality
at the ylide-carbon-atom upon coordination to the metal.[6a]
plexes containing bis(chelating) ylides derived from 1,3-dibro-
moacetone.[10]
Whilst in all these compounds the ylides are bound to the
metal through the ylide-carbon atom, there is one report show-
ing that the reaction of keto-stabilized phosphorus- or arsenic
ylides with [PtCl(dppe)]2[BF4]2 at low temperature affords the
cationic species [PtCl(dppe)(ylide)]BF4, in which the ylide is
O-bound to the metal.[11] In solution however, these com-
pounds transform to the C-bound isomer in a first-order pro-
cess, the kinetics of which were studied by IR spectroscopy
in solution. Thus the coordination chemistry of keto-stabilized
arsenic ylides is to date restricted to compounds containing
SnIV, HgII, PdII, and PtII and none of these derivatives have
been studied by X-ray diffraction (Chart 1).
* Prof. Dr. F. Mohr
E-Mail: fmohr@uni-wuppertal.de
[a] Anorganische Chemie, Fakultät für Mathematik und Naturwissen-
schaften
Bergische Universität Wuppertal
Gaußstr. 20
42119 Wuppertal, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.202000110 or from the au-
thor.
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH &
Co. KGaA. · This is an open access article under the terms of the
Creative Commons Attribution-NonCommercial-NoDerivs Li-
cense, which permits use and distribution in any medium, provided
the original work is properly cited, the use is non-commercial and
no modifications or adaptations are made.
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Given our interest in gold compounds containing C-bound
ligands,[12] we wished to examine the behavior of keto-stabi-
lized arsenic ylides towards gold and to investigate the com-
pounds with modern spectroscopic methods and X-ray diffrac-
tion. The first results of this endeavor are reported herein.
Results and Discussion
Ylides are typically synthesized by deprotonation of an ap-
propriate arsonium salt. In the case of Ph3As, the classical pro-
cedure in a solvent typically requires long reaction times due
to the weak nucleophilicity of Ph3As. We therefore used a sol-
vent-free method, which involved melting together Ph3As with
the appropriate 2-bromoacetophenone at 100 °C.[13] This pro-
cedure afforded the desired arsonium salts in high yields and
purity with simple workup in a short amount of time. Sub-
sequently, the arsonium salts 1a–1c were readily deprotonated
in EtOH using 2.5 m aqueous NaOH as base (Scheme 1).
The resulting keto-stabilized arsenic ylides 2a–2c were char-
acterized by various spectroscopic methods including NMR
spectroscopy, IR spectroscopy and mass spectrometry. In ad-
dition, 2a and 2b were also characterized by single-crystal
X-ray diffraction (see below). The proton NMR spectra of the
compounds readily confirm the formation of the ylides. In par-
ticular, the resonance of the ylidic proton can be observed as
a broad signal at around 4.8 ppm, shifted by about 1.5 ppm
Figure 1. Molecular structures of 2a (top) and 2b (below) Ellipsoids
when compared to that of the arsonium salts. Similarly, in the are drawn at the 30% level. Hydrogen atoms as well as the solvated
13C-NMR spectra the resonance of the ylidic carbon atom is
CH2Cl2 (in 2b) are omitted for clarity.
found at around 58 ppm in the ylides and at approximately
42 ppm in the arsonium salts. A further diagnostic feature of tion, which allowed us to determine their molecular structures
these compounds is the wavenumber of the carbonyl stretching (Figure 1).
frequency. In the ylides this band is shifted by about
Compounds 2a and 2b crystallize in the monoclinic space
100 cm–1 to a lower wavenumber than that in the arsonium groups C2/c and P21/c, respectively. The As–Cylide bond
salts, where the CO stretching frequency falls in the range of lengths of 1.826(2) Å and 1.842(3) Å are slightly longer than
1660 to 1670 cm–1. For the chloro- and nitro-derivatives (2a an arsenic-carbon double bond (1.78 Å) but considerably
and 2b) we obtained single crystals suitable for X-ray diffrac- shorter than an As-C single bond (1.98 Å). Furthermore, the
Scheme 1.
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two carbon atoms adjacent to arsenic (C1 and C2) are
1.375(3) Å and 1.370(5) Å apart, clearly indicative of con-
siderable double bond character. The C–O bond lengths of
1.253(2) Å and 1.255(4) Å are also slightly longer than a car-
bon–oxygen double bond. Thus, these parameters show con-
siderable bond delocalization along the As–C–C–O unit. A
keto-stabilized arsenic ylide may be represented by the three
tautomeric forms a-c illustrated in Figure 2. Tautomer a, the
ylene form, can however be neglected, since the d-orbitals are
too high in energy to be involved in bonding of main group
elements.
Figure 2. Tautomeric forms of a keto-stabilized arsenic ylide.
The bond lengths observed in the solid-state structures there-
fore result from an averaging of all three tautomers. Surpris-
ingly, there are only two other crystal structures of keto-stabi-
lized arsenic ylides deposited in the CCSD: PhC(O)CHAsPh3
and CF3C(O)CHAsPh3.[14] In the former, which is structurally
most similar to 2a and 2b, the bond lengths are close to those
discussed above. Since, the original dataset was recorded at
room temperature,[14a] we wished to have high-quality 150 K
data for better comparison. We therefore also synthesized and
crystallized PhC(O)CHAsPh3. The molecular structure (Figure
S1) and spectroscopic details are included in the Supporting
Information. In our low-temperature structure of
PhC(O)CHAsPh3 the As–Cylide bond length is with 1.846(2) Å
slightly longer than that in 2a and 2b and similarly, the C–C
and C–O bond lengths are slightly longer, being 1.389(3) Å
and 1.268(2) Å, respectively. In all four compounds, the conju-
Figure 3. Molecular structure of 3b. Ellipsoids are drawn at the 30%
level. Hydrogen atoms are omitted for clarity. Only one part of the
disordered Au–Cl unit is shown.
Table 1. Comparison of selected bond lengths /Å, angles /°, and carb-
onyl stretching frequencies /cm–1 in complexes 2b and 3b.
2b
3b
As(1)–C(1)
C(1)–C(2)
C(2)–O(1)
As(1)–C(1)–C(2)
ν(CO)
1.842(3)
1.370(5)
1.255(4)
113.5(3)
1519
1.905(5)
1.473(8)
1.226(7)
108.4(3)
1627
gated As–C–C–O unit is planar and the ylidic carbon is close consistent with the presence of a double bond. Thus, it is the
to being sp2 hybridized, as evidenced by an As–C–C bond tautomeric form c (Figure 2) of the ylide which is dominant:
angle of approximately 119° in 2a, 114° in 2b and 113° in The lone pair at the ylidic carbon coordinates to the metal
PhC(O)CHAsPh3.
center as shown in Figure 4.
The ylides 2a–2c reacted with [AuCl(tht)] [tht = tetra-
hydrothiophene] in CH2Cl2 to give colorless complexes 3a–3c
in varying yields (Scheme 1). Spectroscopically, the wave-
number of the carbonyl stretching frequency as well as the
chemical shift of the ylidic proton resonance are most diagnos-
tic. We managed to obtain X-ray quality crystals of the nitro-
derivative 3b to confirm the molecular structure (Figure 3).
The compound crystallizes in the orthorhombic centrosym-
metric space group Pbcn. Although the compound has a chiral
center at C(1), the crystals are racemic. In the crystal packing
both S- and R-configured molecules can be observed. The mol-
ecule consists of the ylide bound through the carbon atom to
Figure 4. Schematic illustration of the coordination mode of the ylide
to the AuCl unit.
This structure represents the first reported structure of a
gold. The coordination about the gold is completed by a chlor- metal complex containing a keto-stabilized arsenic ylide.
ide ligand. As expected for a gold(I) compound, its coordina- Therefore, we have no related structures to compare our data
tion arrangement is linear with a C–Au–Cl angle of 179.5°. to, however in the gold(I) complex containing the keto-
The bond lengths in the ylide ligand involving the As–C–C–O stabilized phosphorus-ylide [Ph3PCHC(O)CH2C(O)OEt], the
unit are quite different when compared to those of the ylide Au–Cylide bond length of 2.079(3) Å is similar to that observed
2b discussed above (Table 1).
in 3b [2.041(6) Å].[15] As can be seen from the angles about
As can be seen, the As–C and the C–C bonds in 3b are the ylidic carbon atom (ranging from 107.9° to 109.7°), its
now much closer to a single bond and the C–O bond length is geometry is consistent with sp3-hybridized tetrahedral.
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H, CH2), 7.39–7.43 (m, 1 H, p-Ph), 7.48 (t, J = 7.5 Hz, 2 H, m-Ph),
Gold(I) complexes with carbon-based ligands often show lu-
7.63 (dd, J = 8.3, 1.3 Hz, 2 H, o-Ph), 7.68 (t, J = 7.5 Hz, 6 H, m-
Ph3As), 7.71–7.75 (m, 3 H, p-Ph3As), 7.77 (d, J = 8.6 Hz, 2 H, C6H4),
7.93 (dd, J = 8.2, 1.3 Hz, 6 H, o-Ph3As), 8.50 (d, J = 8.5 Hz, 2 H,
C6H4). 13C NMR (151 MHz, CDCl3): δ = 42.86 (CH2), 122.37 (ipso-
Ph3As), 127.31 (o-Ph), 127.57 (C6H4), 128.50 (p-Ph), 128.96 (m-Ph),
130.61 (m-Ph3As), 130.87 (C6H4), 133.11 (o-Ph3As), 133.16 (C6H4),
133.77 (p-Ph3As), 139.49 (ipso-Ph), 147.57 (C6H4), 192.51 (CO). HR
ES-MS: Calcd. for [C32H26OAs]+ 501.1200; found 501.1197. IR
(ATR): ν˜ = 1659 cm–1 ν(CO).
minescence in the solid-state and/or in solution. Examination
of the gold complexes 3a–3c under a UV-light unfortunately
revealed that the solid compounds were not luminescent at
room temperature and also at liquid nitrogen temperature. To
access a wider range of gold complexes, we attempted to re-
move or exchange the chloride-ligand in 3a–3c. Unfortunately,
the complexes proved to be rather unstable and we only ob-
served cleavage of the gold–carbon bond accompanied by for-
mation of decomposition products and metallic gold.
In summary, we prepared a series of keto-stabilized arsenic
ylides and their corresponding gold(I) chloride complexes. The
C-coordination of the ylide to the metal was studied by various
spectroscopic methods and confirmed by X-ray diffraction.
Further studies of this class of compounds are being continued
in our group.
Preparation of the Ylides: To a solution of the arsonium salt in EtOH
(10 mL) was added NaOH (2.5 m aqueous solution) causing immediate
precipitation of a solid. The solid was isolated by filtration and was
washed well with water and subsequently dried in vacuo.
4-ClC6H4C(O)CHAsPh3 (2a): This was prepared as described above
from 1a (0.840 g, 1.55 mmol). The product was isolated as a beige
1
solid in 60% yield. H NMR (600 MHz, CDCl3): δ = 4.72 (br. s, 1 H,
CH), 7.33 (d, J = 8.5 Hz, 2 H, C6H4), 7.52 (t, J = 7.3 Hz, 6 H, m-
Ph3As), 7.58 (t, J = 7.3 Hz, 3 H, p-Ph3As), 7.72 (d, J = 7.1 Hz, 6 H,
o-Ph3As), 7.91 (d, J = 8.5 Hz, 2 H, C6H4). 13C NMR (151 MHz,
CDCl3): δ = 58.16 (CH), 127.47 (C6H4), 128.83 (ipso-Ph3As), 128.96
(C6H4), 129.49 (o-Ph3As), 131.73 (p-Ph3As), 132.53 (m-Ph3As),
133.19 (C6H4), 137.64 (C6H4), 181.61 (CO). HR ES-MS: Calcd. for
[C26H20ClOAs + H]+ 459.0497; found 459.0449. IR (ATR): ν˜ =
1576 cm–1 ν(CO). X-ray quality crystals were obtained by vapor dif-
fusion using a combination of CH2Cl2 and cyclopentane.
Experimental Section
General: Unless specified otherwise, reactions were carried out under
dinitrogen gas using HPLC grade solvents dried with 3 Å molecular
sieves. [AuCl(tht)] (tht = tetrahydrothiophene) was prepared by a pub-
lished method.[16] All other chemicals and solvents were commercial
products and were used as received. NMR spectra were recorded on
Bruker Avance 400 or Bruker Avance III 600 instruments. Spectra
were referenced externally to Me4Si. IR spectra were measured on a
Nicolet iS5 spectrometer equipped with an iD5 diamond ATR unit.
High-resolution electrospray mass spectra were measured on a Bruker
Daltonics micrOTOF instrument.
4-O2NC6H4C(O)CHAsPh3 (2b): This was prepared as described
above from 1b (0.845 g, 1.54 mmol). The product was isolated as a
bright yellow solid in 80% yield. 1H NMR (600 MHz, CDCl3): δ =
4.80 (br. s, 1 H, CH), 7.55 (t, J = 7.5 Hz, 6 H, m-Ph3As), 7.59–7.63
(m, 3 H, p-Ph3As), 7.71–7.75 (m, 6 H, o-Ph3As), 8.11 (d, J = 8.9 Hz,
2 H, C6H4), 8.22 (d, J = 8.9 Hz, 2 H, C6H4). 13C NMR (151 MHz,
CDCl3): δ = 59.79 (CH), 123.10 (C6H4), 127.78 (C6H4), 128.05 (ipso-
Ph3As), 129.63 (o-Ph3As), 132.01 (p-Ph3As), 132.42 (m-Ph3As),
146.58 (C6H4), 148.13 (C6H4), 178.98 (CO). HR ES-MS: Calcd. for
[C26H20NO3As + H]+ 470.0737; found 470.0735. IR (ATR): ν˜ =
1519 cm–1 ν(CO). Large yellow crystals for X-ray diffraction were
obtained by crystallization from a mixture of CH2Cl2 and Et2O.
Preparation of the Arsonium Salts: Ph3As (0.500 g, 1.64 mmol) was
heated to 100 °C (heating block temperature) in an open vessel. Once
the material had completely melted, the 2-bromoacetophenone deriva-
tive (1.2 equiv.) was added. After ca. 30 min the melt was left to cool
to room temperature. The resulting solid was dissolved in CH2Cl2
(5 mL) and Et2O (50 mL) was added causing precipitation of the prod-
uct. The solid was isolated by filtration and was washed with Et2O
(3ϫ10 mL) and subsequently dried in vacuo.
[4-ClC6H4C(O)CH2AsPh3]Br (1a): The product was isolated in 96%
1
yield as a colorless solid. H NMR (400 MHz, CDCl3): δ = 6.47 (s, 2
H, CH2), 7.51 (d, J = 8.7 Hz, 2 H, C6H4), 7.68 (t, J = 7.5 Hz, 6 H, m-
Ph3As), 7.72–7.76 (m, 3 H, p-Ph3As), 7.92 (dd, J = 8.6, 1.1 Hz, 6 H,
o-Ph3As), 8.41 (d, J = 8.7 Hz, 2 H, C6H4). 13C NMR (101 MHz,
CDCl3): δ = 42.76 (CH2), 122.23 (ipso-Ph3As), 129.39 (C6H4), 130.66
(m-Ph3As), 131.75 (C6H4), 132.87 (C6H4), 133.11 (o-Ph3As), 133.85
(p-Ph3As), 141.81 (C6H4), 192.07 (CO). HR ES-MS: Calcd. for
4-PhC6H4C(O)CHAsPh3 (2c): This was prepared as described above
from 1c (0.375 g, 0.64 mmol). The product was isolated as a pale red
solid in 64% yield. 1H NMR (400 MHz, CDCl3): δ = 4.81 (s, 1 H,
CH), 7.36 (t, J = 7.8 Hz, 1 H, p-Ph), 7.46 (t, J = 7.7 Hz, 2 H, m-Ph),
7.53 (t, J = 7.5 Hz, 6 H, m-Ph3As), 7.59 (t, J = 7.4 Hz, 3 H, p-Ph3As),
7.63 (d, J = 8.1 Hz, 2 H, C6H4), 7.66 (dd, J = 8.3, 1.1 Hz, 2 H, o-Ph),
7.77 (dd, J = 8.0, 1.6 Hz, 6 H, o-Ph3As), 8.08 (d, J = 8.1 Hz, 2 H,
C6H4). 13C NMR (101 MHz, CDCl3): δ = 57.33 (CH), 126.50 (C6H4),
127.15 (o-Ph), 127.20 (p-Ph), 127.46 (C6H4), 128.68 (ipso-Ph3As),
128.89 (m-Ph), 129.46 (m-Ph3As), 131.68 (p-Ph3As), 132.52 (o-
Ph3As), 139.30 (ipso-Ph), 141.12 (C6H4), 141.79 (C6H4), 181.40 (CO).
HR ES-MS: Calcd. for [C32H25OAs + H]+ 501.1200; found 501.1207.
IR (ATR): ν˜ = 1567 cm–1 ν(CO).
[C26H21ClOAs]+ 459.0497; found 459.0449. IR (ATR): ν˜
1663 cm–1 ν(CO).
=
[4-O2NC6H4C(O)CH2AsPh3]Br (1b): The product was isolated in
95% yield as a pale yellow solid. 1H NMR (600 MHz, CDCl3): δ =
6.63 (s, 2 H, CH2), 7.65 (t, J = 7.6 Hz, 6 H, m-Ph3As), 7.72 (t, J =
7.5 Hz, 3 H, p-Ph3As), 7.92 (d, J = 7.1 Hz, 6 H, o-Ph3As), 8.22 (d,
J = 8.9 Hz, 2 H, C6H4), 8.63 (d, J = 8.9 Hz, 2 H, C6H4). 13C NMR
(151 MHz, CDCl3): δ = 42.61 (CH2), 121.80 (ipso-Ph3As), 123.84
(C6H4), 130.66 (m-Ph3As), 131.48 (C6H4), 133.02 (o-Ph3As), 133.91
(p-Ph3As), 138.80 (C6H4), 150.99 (C6H4), 192.18 (CO). HR ES-MS:
Calcd. for [C26H21NO3As]+ 470.0737; found 470.0733. IR (ATR):
ν˜ = 1671 cm–1 ν(CO).
Preparation of the Gold(I) Complexes: To an ice-cooled solution of
the respective ylide (0.5 mmol) in CH2Cl2 (10 mL) was added
[AuCl(tht)] (0.160 g, 0.5 mmol). The mixture was left to stir at room
temperature protected from light for ca. 24 h. Addition of Et2O
(50 mL) caused precipitation of the product. The solid was isolated by
[4-PhC6H4C(O)CH2AsPh3]Br (1c): The product was isolated in 66% filtration and was washed with Et2O (3ϫ10 mL) and subsequently
1
yield as a yellow solid. H NMR (600 MHz, CDCl3): δ = 6.47 (s, 2 dried in vacuo.
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Table 2. Crystallographic and refinement details for compounds 2a, 2b and 3b.
2a
2b
3b
Empirical formula
Color
C26H20AsClO
colorless
458.79
0.71073
monoclinic
C2/c
C27H22AsCl2NO3
yellow
554.27
0.71073
monoclinic
P21/c
C26H20AsAuClNO3
colorless
701.77 g/mol
0.71073
orthorhombic
Pbcn
Formula weight /g·mol–1
Wavelength /Å
Crystal system
Space group
Unit cell dimensions
a /Å
b /Å
c /Å
α /°
16.8053(5)
11.0627(4)
23.7443(7)
90.0
8.9714(3)
24.5525(12)
10.6633(3)
18.8241(5)
90.0
18.6537(6)
15.0625(4)
103.97(3)
β /°
100.286(3)
90.0
4343.4(2)
103.907(3)
90.0
2446.82(13)
4
1.505
1.638
90.0
90.0
4928.3(3)
8
1.892
γ /°
Volume /Å3
Z
8
ρcalc /g·cm–3
1.403
1.702
μ /mm–1
7.439
F(000)
1872.0
1128.0
2688.0
Crystal size /mm
2θ range for data collection /°
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I Ͼ 2σ(I)]
Final R indices [all data]
Largest difference peak/hole /e·Å–3
0.05ϫ0.10ϫ0.13
4.92 to 59.286
11726
5051 [Rint = 0.0209]
5051/0/262
1.034
R1 = 0.0320, wR2 = 0.0676
R1 = 0.0471, wR2 = 0.0742
0.28/–0.36
0.05ϫ0.07ϫ0.12
5.18 to 59.05
13437
5805 [Rint = 0.0307]
5805/0/307
1.075
R1 = 0.0492, wR2 = 0.1224
R1 = 0.0678, wR2 = 0.1327
1.46/–1.21
0.02ϫ0.04ϫ0.07
4.694 to 58.968
18053
5844 [Rint = 0.0550]
5844/0/316
1.040
R1 = 0.0452, wR2 = 0.0700
R1 = 0.0850, wR2 = 0.0802
0.79/–0.96
[AuCl{4-ClC6H4C(O)CHAsPh3}] (3a): The product was isolated in absorption correction was carried out using the CrysAlis Pro program
28% yield as a colorless solid. 1H NMR (600 MHz, CDCl3): δ = 5.17
(s, 1 H, CH), 7.40 (d, J = 8.6 Hz, 2 H, C6H4), 7.57 (t, J = 7.5 Hz, 6
H, m-Ph3As), 7.64–7.69 (m, 3 H, p-Ph3As), 7.79 (dd, J = 8.2, 1.1 Hz,
6 H, o-Ph3As), 8.12 (d, J = 8.6 Hz, 2 H, C6H4). The material was not
soluble enough to obtain a meaningful 13C NMR spectrum. IR (ATR):
ν˜ = 1622 cm–1 ν(CO).
package.[17] The structures were solved using SHELXT[18] and refined
with SHELXL[19] operated through the Olex2 interface.[20] Crystallo-
graphic and refinement details are collected in Table 2. During refine-
ment of the structure 3b it became apparent that the Au–Cl unit is
disordered over two positions, which was best modeled with a 50:50
occupancy for each gold and chloride atom. In addition, there was
evidence for highly disordered residual solvent molecules, for which
we were unable to develop a suitable model. The data was therefore
subjected to the Solvent Mask procedure implemented in Olex2.[20]
[AuCl{4-O2NC6H4C(O)CHAsPh3}] (3b): The product was isolated
1
in 64% yield as a colorless solid. H NMR (600 MHz, CDCl3): δ =
5.08 (s, 1 H, CH), 7.55–7.62 (m, 6 H, m-Ph3As), 7.69–7.75 (m, 3 H,
p-Ph3As), 7.78–7.90 (m, 6 H, o-Ph3As), 8.25 (d, J = 8.8 Hz, 2 H,
C6H4), 8.32 (d, J = 8.8 Hz, 2 H, C6H4). 13C NMR (151 MHz, CDCl3):
δ = 59.94 (CH), 123.12 (C6H4), 127.78 (C6H4), 128.04 (ipso-Ph3As),
129.64 (m-Ph3As), 132.03 (p-Ph3As), 132.43 (o-Ph3As), 146.56
(C6H4), 147.96 (C6H4), 179.01 (CO). IR (ATR): ν˜ = 1627 cm–1 ν(CO).
X-ray quality crystals were obtained by vapor diffusion using a combi-
nation of CH2Cl2 and cyclopentane.
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK.
Copies of the data can be obtained free of charge on quoting
the depository numbers CCDC-1964292 (2a), CCDC-1971090 (2b),
and CCDC-1964291 (3b) (Fax: +44-1223-336-033; E-Mail:
deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk)
Supporting Information (see footnote on the first page of this article):
Crystallographic details and copies of NMR spectra.
[AuCl{4-PhC6H4C(O)CHAsPh3}] (3c): The product was isolated in
74% yield as a colorless solid. 1H NMR (400 MHz, CDCl3): δ = 5.30
(s, 1 H, CH), 7.41 (t, J = 7.3 Hz, 1 H, p-Ph), 7.48 (t, J = 7.5 Hz, 2 H,
m-Ph), 7.57 (t, J = 7.5 Hz, 6 H, m-Ph3As), 7.60–7.70 (m,7 H, o-Ph, p-
Ph3As, C6H4), 7.82 (d, J = 7.1 Hz, 6 H, o-Ph3As), 8.25 (d, J = 8.4 Hz,
2 H, C6H4). 13C NMR (101 MHz, CDCl3): δ = 39.88 (CH), 126.53
(ipso-Ph3As), 127.10 (o-Ph), 127.28 (C6H4), 128.13 (p-Ph), 128.90 (m-
Ph), 129.22 (C6H4), 130.01 (m-Ph3As), 132.76 (p-Ph3As), 132.85 (o-
Ph3As), 134.72 (ipso-Ph), 139.99 (C6H4), 145.70 (C6H4), 195.69 (CO).
IR (ATR): ν˜ = 1615 cm–1 ν(CO).
Acknowledgements
Open access funding enabled and organized by Projekt DEAL.
Keywords: Arsonium salts; Gold; Ylide
X-ray Crystallography: Diffraction data was collected at 150 K (2b,
3b) or room temperature (2a) using a Rigaku Oxford Diffraction Gem-
ini Ultra diffractometer, equipped with an EOS CCD area detector and
a four-circle kappa goniometer. Data integration, scaling and empirical
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Received: March 3, 2020
Published Online: April 20, 2020
Z. Anorg. Allg. Chem. 2020, 889–894
www.zaac.wiley-vch.de
894
© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim