The crystal and molecular structures of gold(I) complexes containing the electron-rich P-Donor ligand Ph3PNPPh2

Article abstract of DOI:10.1002/zaac.201100006

The reaction of [AuCl(tht)] (tht = tetrahydrothiophene) with an equimolar amount of the electron-rich ligand N-diphenylphosphino-triphenylphosphinimine, Ph₃PNPPh₂, in THF afforded the new complex [AuCl(Ph ₃PNPPh₂)] (1) in good yield. Furthermore, the reaction of [AuHCl₄] with Ph₃PNPPh₂ in a molar ratio of 1:3 in dichloromethane at room temperature yielded the complex salt [Au(Ph ₃PNPPh₂)₂]Cl (2) as the dichloromethane solvate beside Ph₃PNPPh₂Cl₂ as the side-product of oxidation. The molecular structures of metal complexes 1 and 2 were determined by single-crystal X-ray diffraction. Because of the bulkiness of the ligand Ph₃PNPPh₂ no short intermolecular gold-gold interactions (aurophilic aggregation) could be observed in the solid-state structures. Copyright

Full text of DOI:10.1002/zaac.201100006

ARTICLE
DOI: 10.1002/zaac.201100006
The Crystal and Molecular Structures of Gold(I) Complexes Containing the
Electron-Rich P-Donor Ligand Ph3PNPPh2
Hans-Christian Böttcher,[a] Karin Lux,[a] Mustafa Kidik,[a] and
Konstantin Karaghiosoff*[a]
Dedicated to Professor Peter Klüfers on the Occasion of His 60th Birthday
Keywords: Gold; Organophosphorus ligands; Crystal structure; P-Donors; NMR spectroscopy
Abstract. The reaction of [AuCl(tht)] (tht = tetrahydrothiophene) with (2) as the dichloromethane solvate beside Ph3PNPPh2Cl2 as the side-
an equimolar amount of the electron-rich ligand N-diphenylphosphino- product of oxidation. The molecular structures of metal complexes 1
triphenylphosphinimine, Ph3PNPPh2, in THF afforded the new com-
and 2 were determined by single-crystal X-ray diffraction. Because of
plex [AuCl(Ph3PNPPh2)] (1) in good yield. Furthermore, the reaction the bulkiness of the ligand Ph3PNPPh2 no short intermolecular gold–
of [AuHCl4] with Ph3PNPPh2 in a molar ratio of 1:3 in dichlorometh- gold interactions (aurophilic aggregation) could be observed in the
ane at room temperature yielded the complex salt [Au(Ph3PNPPh2)2]Cl solid-state structures.
which resulted in the formation of the complex salt
Introduction
[Au(tBu2PH)2][HCl2] in good yield.[9]
In the last years, the interest in the chemistry of gold has
Herein we describe investigations on the reaction of a gold(I)
grown immensely because of many applications of compounds
and a gold(III) precursor compound with the electron-rich ligand
containing this element in the fields of catalysis, materials sci-
N-diphenylphosphino-triphenylphosphinimine (Ph3PNPPh2) re-
ence, and medicine. An introductory perspective in this fasci-
sulting in the new compounds [AuCl(Ph3PNPPh2)] (1) and
nating research area was given recently by Hutchings, Brust,
[Au(Ph3PNPPh2)2]Cl (2), respectively, the crystal structures of
and Schmidbaur.[1] Current investigations show that gold spe-
which were determined by single-crystal X-ray diffraction.
cies are interesting anticancer drug candidates with a mode of
action different from that of well-established platinum agents.
In this context, the spectrum of gold complexes described as
antiproliferative compounds comprises a broad variety of dif-
ferent species including many phosphane complexes.[2] In ad-
dition, gold(I) compounds containing phosphane ligands are of
special importance due to their characteristic luminescence as
well as unique photophysical and photochemical properties.[3]
Homogeneous gold catalysts are playing an increasing role in
organic synthesis, whereby standard catalysts in this field are
complexes of the type [Au(PR3)X] (X = typically Cl).[4] Today
there is an active interest in studies on the synthesis of such
complexes using sterically demanding organophosphorus li-
gands, e.g.[5–7] Currently we are interested in the reaction be-
havior of transition metal complexes towards sterically de-
manding phosphane ligands such as tBu2PH.[8] In this context
we studied the reaction of hydrogen tetrachloridoaurate(III)
hydrate with tBu2PH in dichloromethane at room temperature,
Results and Discussion
Synthesis of AuI Complexes 1 and 2
Treatment of equimolar amounts of [AuCl(tht)] (tht = tetra-
hydrothiophene) with Ph3PNPPh2 in THF afforded a clear col-
orless solution. During stirring for 2 h at room temperature a
colorless precipitate was obtained, the amount of which in-
creased upon further stirring overnight (Scheme 1).
Scheme 1. Synthesis of 1.
After workup (see Experimental Section) colorless crystals
suitable for an X-ray diffraction study were grown at room
temperature from a CH2Cl2/n-heptane mixture by slow diffu-
sion overnight. Elemental analysis and the NMR spectroscopic
data of the new compound were consistent with the presence
of the complex [AuCl(Ph3PNPPh2)] (1).
* Prof. Dr. K. Karaghiosoff
Fax: +49-89-2180-77398
E-Mail: klk@cup.uni-muenchen.de
[a] Department of Chemistry
Ludwig Maximilian University of Munich
Butenandtstr. 5–13 (D)
Furthermore, the reaction of solid hydrogen tetrachloridoau-
rate(III) hydrate with three equivalents of Ph3PNPPh2 in di-
81377 München, Germany
Z. Anorg. Allg. Chem. 2011, 637, 353–356
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
353

H.-C. Böttcher, K. Lux, M. Kidik, K. Karaghiosoff
ARTICLE
Table 1. 13C{1H} NMR spectroscopic data of compounds 1 and 2 re-
corded in CH2Cl2 (coupling constantsa) J in Hz).
chloromethane at room temperature yielded immediately a
clear colorless solution. After stirring overnight to complete
the reaction, a colorless solid was obtained from this solution
by precipitation with n-heptane, which was identified by ele-
mental analysis and spectroscopic methods as the complex salt
[Au(Ph3PNPPh2)2]Cl (2) (see Scheme 2, labeling scheme of
complexes 1 and 2 see Figure 1).
1
2a)
δ13C
C1
139.8
131.4
128.4
130.5
129.3
132.7
128.9
132.7
74.6
104.6
15.4
10.4
12.3
2.7
139.1
131.0
128.8
130.9
129.3
132.3
129.0
132.9
70.7
104.4
16.1
10.5
11.9
2.7
C2
C3
C4
C5
C6
C7
C8
1JPC
2JPC
3JPC
P1C1
P2C5
P1C2
P2C6
P1C3
P1C5
P2C1
P2C7
P1C4
P1C6
P2C8
Scheme 2. Synthesis of 2.
7.6
7.5
12.7
2.7
12.7
2.3
4JPC
0.6
–
3.0
2.9
a) N = |JAX + JAX'| ≈ JAX.
Figure 1. Labeling scheme of complexes 1 and 2.
Crystal and Molecular Structures of 1 and 2
Single crystals of 1 and 2, respectively, suitable for X-ray
diffraction studies were obtained by slow diffusion of n-hep-
tane into a concentrated dichloromethane solution at room tem-
perature overnight. Complex 1 crystallizes in the monoclinic
space group P21/c with four molecules in the unit cell. The
coordination sphere at the gold atom can be considered as two-
coordinate linear. A view of the molecule is shown in Figure 2,
selected bond lengths and angles are given in the caption.
As outlined in the reaction scheme, during this reaction AuIII
is reduced to AuI and the excess of the organophosphorus li-
gand is oxidized to Ph3PNPPh2Cl2. Similar observations were
made in analogous reactions starting from AuCl3 and PPh3.[10]
Alternatively, complex 2 can be obtained with better yield
(74 %) starting from the gold(I) complex AuCl(tht), which is
reacted with two equivalents of the ligand Ph3PNPPh2.
31P{1H} and 13C{1H} NMR Spectroscopy of 1 and 2
The 31P{1H} NMR spectrum of 1 in CD2Cl2 exhibited two
doublets at 47.3 and 19.9 ppm (2JPP = 23.3 Hz). In comparison
with the 31P NMR spectroscopic data of the known complex
[AuCl(PPh3)] (δ = 33.0, s, CDCl3[11]) a downfield shift is ob-
served exhibiting the Ph3PNPPh2 ligand as a more electron
rich P-donor ligand than PPh3. The latter effect is caused by
the stronger electron donating properties of the Ph3PN substit-
uent. The presence of Ph3PNPPh2Cl2 could be confirmed by
us using 31P NMR spectroscopy. The 31P{1H} NMR spectrum
of 2 in CD2Cl2 showed two triplet signals at 67.3 and 19.3 ppm
(N
= 27 Hz = + a linear complex
2JPP 4JPP). For
[Au(Ph3NPPh2)2]+ an AA'XX' spin system is expected. Due to
the very small P–P coupling between the PR3 terminal phos-
phorus atoms and the relatively large JPP coupling between
Figure 2. Molecular structure of [AuCl(Ph3PNPPh2)] (1) in the crystal
(ORTEP drawing with 50 % probability ellipsoids, hydrogen atoms
are omitted for clarity). Selected distances /Å and angles /°: Au1–P1
2.2334(12), Au1–Cl1 2.2928(12), P1–N1 1.621(4), P1–C1 1.815(5),
P1–C7 1.830(4), P2–N1 1.573(4), P2–C13 1.801(4), P2–C19 1.792(5),
P2–C25 1.898(5); P1–Au1–Cl1 177.47(5), N1–P1–C1 104.1(2), N1–
P1–C7 104.68(19), C1–P1–C7 105.9(2), N1–P1–Au1 120.88(13), C1–
P1–Au1 110.68(15), C7–P1–Au1 109.48(15), N1–P2–C13 114.6(2),
N1–P2–C19 106.8(2).
2
the PPh2 phosphorus atoms, the expected ten line pattern for
the A (and X) part is reduced to a deceptively simple three line
pattern, from which only the N value (27 Hz) can be obtained.
Similarly as described for compound 1, also in this case a sig-
nificant downfield shift is observed by comparison with the
31P NMR spectroscopic data of [Au(PPh3)2]Cl (δ = 39.0, s,
CDCl3[11]). This downfield shift is indicative of the electron-
rich character of the ligand Ph3PNPPh2 (vide supra) (13C{1H}
NMR spectroscopic data see Table 1).
The molecular structure is closely related to that of
[AuCl(PPh3)].[12] For the latter the following important struc-
354
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© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 353–356

Gold(I) Complexes with Electron-Rich P-Donor Ligand Ph3PNPPh2
tural parameters were found: Au–P 2.235(3), Au–Cl ganophosphorus ligands were reported: [Au(PAd2Bn)2]+ (Ad =
2.279(3) Å; P–Au–Cl 179.63(8)°. These data agree well with 1-adamantyl, Bn
=
benzyl),[5] [Au(tBu3P)2]+[16] or
the observed ones for complex 1 (see Figure caption). Further- [Au(Mes3P)2]+ (Mes = mesityl).[17] Important bonding parame-
more, the structural parameters of 1 are similar to the observed ters of the latter compounds also agree well with the observed
ones for compounds containing electron-rich organophospho- ones in 2: Au1–P1 2.3348(9) Å, P1–Au–P1' 180.00° for
rus ligand as [AuCl(PAd2nBu)] (Ad = 1-adamantyl or nBu = [Au(Ad2BnP)2]+, Au1–P1 2.323(2), Au1–P2 2.321(2) Å, P1–
n-butyl)[5] and [AuCl(tBu2PH)][13] for example. Important Au–P2 180.0° for [Au(tBu3P)2]+, and Au–P 2.3525(10) Å, P–
bonding parameters of the latter species are: Au1–P1 Au–P' 179.72(7)° for the complex [Au(Mes3P)2]+.
2.2674(6), Au1–Cl1 2.3107(6) Å, P1–Au1–Cl1 177.07(2)° for
[AuCl(Ad2nBu)] and Au–P 2.230(2), Au–Cl 2.284(3) Å, P– (greater than 5 Å). This suggests that there are no attractive
Au–Cl 176.5(1)° for [AuCl(tBu2PH)]. interactions between the gold atoms in the solid state since the
The Au···Au separations in both complexes are quite large
Complex 2 crystallizes in the monoclinic space group P21/c organophosphorus ligands appear to be too bulky to allow the
with four molecules in the unit cell. The coordination sphere metal atoms to associate.
at the gold atom can be considered as two-coordinate linear. A
view of the cation of the complex salt [Au(Ph3PNPPh2)2]Cl
Conclusions
(2) is shown in Figure 3, selected bond lengths and angles are
given in the caption.
A
convenient synthesis for the new compounds
[AuCl(Ph3PNPPh2)] (1) and [Au(Ph3PNPPh2)2]Cl (2) were de-
veloped and their molecular structures were confirmed by X-
ray crystal structure analysis. In the solid state, for both com-
pounds no attractive interactions between the gold atoms (au-
rophilic aggregation) could be observed presumably because
of the bulkiness of the used organophosphorus ligands.
Experimental Section
General: All manipulations were carried out under dry argon using
standard Schlenk techniques. Solvents were dried according to stand-
ard procedures and stored under nitrogen. Hydrogen tetrachloroau-
rate(III) hydrate was purchased from ABCR. Complex [AuCl(tht)][18]
[19]
and ligand Ph3PNPPh2 were prepared according to literature proce-
dures. 1H, 13C, and 31P{1H} NMR spectra were recorded with Jeol
Eclipse 270 and Jeol EX 400 instruments operating at 270 and
400 MHz (1H), at 68 and 100 MHz (13C), and at 109 and 161 MHz
(31P), respectively. Elemental analyses (C, H, N, Cl) were performed
by the Microanalytical Laboratory of the Department of Chemistry,
LMU Munich, with a Heraeus Elementar Vario El instrument. Melting
Points were measured in sealed capillaries under argon with a Büchi
B540 instrument.
Figure 3. Structure of the cation of [Au(Ph3PNPPh2)2]Cl·2CH2Cl2 (2)
in the crystal (ORTEP drawing with 50 % probability ellipsoids, hy-
drogen atoms are omitted for clarity). Selected distances /Å and an-
gles /°: Au1–P1 2.320(2), Au1–P3 2.322(2), P1–N1 1.656(8), P1–C1
1.793(13), P1–C7 1.827(9), P2–N1 1.532(7), P2–C13 1.802(9), P2–
C19 1.810(9), P2–C25 1.812(9), P3–N2 1.631(8), P3–C31 1.813(9),
P3–C37 1.808(9), P4–N2 1.637(8), P4–C43 1.802(10), P4–C49
1.800(9), P4–C55 1.802(9); P1–Au1–P3 179.42(10), N1–P1–C1
105.9(4), N1–P1–C7 107.7(4), N1–P2–C13 113.6(4), N1–P2–C19
113.6(4), N1–P2–C25 107.3(4), C13–P2–C19 106.9(4), N1–P1–Au1
115.7(3), C1–P1–Au1 110.8(3), C7–P1–Au1 111.3(3), N2–P3–Au1
118.3(3), P1–N1–P2 125.8(5), P3–N2–P4 120.3(5).
X-ray Crystal Structure Determination: Single crystals of 1 and 2,
respectively, were placed on perfluorinated oil. A suitable crystal was
selected by means of a polarization microscope and mounted on the
tip of a glass fiber. Data collection was performed with an Oxford
XCalibur diffractometer using Mo-Kα radiation (λ = 0.71073 Å). The
structure was solved by Direct Methods (SIR97)[20] and refined by full-
matrix least-squares calculations on F2 (SHELXL-97).[21] Anisotropic
displacement parameters were refined for all non-hydrogen atoms. De-
tails of crystal data, data collection, structure solution, and refinement
parameters of 1 and 2 are summarized in Table 2.
The molecular structure of the cation of 2 is closely related
to cation [Au(PPh3)2]+ in the compounds [Au(PPh3)2]X (X =
PF6 or NO3 ).[14] Thus, important bonding parameters of the
latter compounds agree well with the observed ones in 2: Au–
P1 2.314(2), Au–P2 2.309(2) Å, P1–Au–P2 177.4(1)° for
[Au(PPh3)2]PF6 and Au–P1 2.312(4), Au–P2 2.311(2) Å, P1–
Au–P2 171.1(2)° for [Au(PPh3)2]NO3. Furthermore, the crystal
structures of [Au(PPh3)2]BF4 and [Au(PPh3)2][C(CN)3] were
reported.[15] For the latter compounds the following data were
found: Au–P1 2.321(3), Au–P2 2.322(3) Å, P1–Au–P2
167.3(1)° for [Au(PPh3)2]BF4 and Au–P 2.315(2) Å, P–Au–P'
180° for [Au(PPh3)2][C(CN)3], which are also in a good agree-
ment with the observed data for 2. Several other crystal struc-
–
–
Crystallographic data for the structures in this paper have been depos-
ited with the Cambridge Crystallographic Data Centre as supplemen-
tary publication CCDC-748585 (1) and CCDC-748586 (2). Copies of
the data can be obtained free of charge on application to CCDC, 12
Union Road, Cambridge CB21EZ, UK (Fax: +44-1223-336033;
E-Mail: deposit@ccdc.cam.ac.uk).
Synthesis of [AuCl(Ph3PNPPh2)] (1) from [AuCl(tht)]: To a slurry
tures of closely related complexes containing electron-rich or- of [AuCl(tht)] (321 mg, 1 mmol) in THF (20 mL) the ligand
Z. Anorg. Allg. Chem. 2011, 353–356
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
355

H.-C. Böttcher, K. Lux, M. Kidik, K. Karaghiosoff
ARTICLE
Table 2. Details of the X-ray data collection and refinement for 1 and 2.
Ph3PNPPh2 (462 mg, 1 mmol) was added at room temperature and
the mixture was stirred overnight. The resulting colorless solution was
evaporated to dryness in vacuo. The remaining residue was crystallized
from CH2Cl2/n-heptane (1:10) as colorless crystals. The precipitate
was filtered off, washed three times with n-pentane (10 mL portions)
and dried in vacuo. Yield 428 mg (74 %).
1
2
Formula
C30H25AuClNP2
693.9
C62H54AuCl5N2P4
1325.2
Mr
Temperature /°C
Crystal system
Space group
a /Å
200
200
monoclinic
P21/c
monoclinic
P21/c
10.3451(2)
14.6615(3)
17.7018(4)
97.367(2)
2662.75(10)
4
18.9172(4)
13.0705(2)
24.4936(5)
106.822(2)
5797.1(2)
4
b /Å
Acknowledgement
The authors are grateful to the Department of Chemistry, Ludwig Maxi-
milian University of Munich, for financial support of this work.
c /Å
β /deg
V /Å3
Z
Dcalcd /g·cm–3
μ(Mo-Kα) /mm–1
F(000), e
θ range for data
collection /deg
hkl range
1.731
1.518
5.765
2.920
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1
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Received: January 3, 2011
Published Online: February 20, 2011
356
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© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 353–356