Organogold(I) complexes: Synthesis, X-ray crystal structures and aurophilicity

Article abstract of DOI:10.1016/j.jorganchem.2005.07.080

The synthesis of RAuPPh₃ (R = aryl) from ClAuPPh₃ and Grignard RM reagents (M = Li or MgX) is described. New (vinylphenyl)gold(I) and other arylgold(I) complexes were characterized by ¹H, ¹³C, ³¹P,

Full text of DOI:10.1016/j.jorganchem.2005.07.080

Journal of Organometallic Chemistry 690 (2005) 4835–4843
www.elsevier.com/locate/jorganchem
Organogold(I) complexes: Synthesis, X-ray crystal
structures and aurophilicity
a
b
c
C. Croix a,b, A. Balland-Longeau , H. Allouchi , M. Giorgi ,
b
b,
*
A. Ducheˆne , J. Thibonnet
a
CEA Le Ripault, Materials Department, BP 16, 37260 Monts, France
b
`
Laboratoire de Synthese et Physicochimie Organique et Therapeutique, Faculte des Sciences de Tours, Parc de Grandmont, 37200 Tours, France
c
´
´
Laboratoire de Cristallochimie et Laboratoire de Bio-inorganique Structurale, Universite´ Paul Ce´zanne Aix-Marseille III, F.S.T.
ˆ
Saint-Je´rome, Service 432, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France
Received 11 April 2005; received in revised form 21 July 2005; accepted 25 July 2005
Available online 16 September 2005
Abstract
The synthesis of RAuPPh3 (R = aryl) from ClAuPPh3 and Grignard RM reagents (M = Li or MgX) is described. New (vinyl-
1
phenyl)gold(I) and other arylgold(I) complexes were characterized by H, 13C, 31P, 19F NMR, melting point determination, and
X-ray diffraction. Crystallographic studies of some organogold(I) complexes indicate an aurophilic Au(I)ꢀ ꢀ ꢀAu(I) attraction.
Ó 2005 Elsevier B.V. All rights reserved.
Keywords: Organogold(I) complexes; Aurophilicity; X-ray diffraction
1. Introduction
with high level of homogeneity [2] for producing various
doped materials.
Inertial confinement fusion (ICF) is a subject of in-
tense investigations. In ICF, energetic driver beams
These doped materials must answer to several
requirements as follows: (1) a composition including
carbon, hydrogen and a controlled amount of gold
atom, with tolerance of phosphorous atom, (2) an
homogeneous repartition of gold into the polymer or
foams (3) controlled physical properties. To reach these
materials, it was essential to prepare monomers contain-
ing gold that were ‘‘air and water stable’’ then could be
easily handled.
The substituted polystyrenes family was excellent
candidate for such applications because of their atomic
composition and the large chemistry that it offers. We
have previously described the synthesis of polymerizable
monomers: some substituted styrene derivatives and
their corresponding polymers containing silicium, ger-
manium and tin [1]. Then in this work, we choose to
synthesize substituted styrenes derivatives containing
gold that must be easily copolymerized via radical
´
from high power laser (Laser MegaJoule) and X-ray
heat a target containing specific materials in some parts.
Organic and organometallic materials (polymers or alve-
olar materials also called foams) are frequently used as
parts of targets for various experiments of plasma phys-
ics: plasma propagation, laser interaction with matter,
etc). In this field, the development of polymerizable
monomers containing specific atoms such as group
XIV (Si, Ge and Sn) or group XI transition metals is a
very important theme [1]. In this new study, the ‘‘gold’’
atom must be introduced by covalent bond into the
monomers structure. Such monomers containing gold
must be further polymerized or introduced in foams
*
Corresponding author. Tel.: +247367359; fax: +247367073.
E-mail address: jerome.thibonnet@univ-tours.fr (J. Thibonnet).
0022-328X/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.07.080

4836
C. Croix et al. / Journal of Organometallic Chemistry 690 (2005) 4835–4843
Table 1
Structures of gold complexes
polymerization process: with styrene to prepare various
polymers or with a mixture of styrene/DVB to prepare
foams by an high internal phase emulsion (HIPE) [3].
The organometallic chemistry of gold has attracted
much attention [4–6] during past decades. Two types
of organogold compounds can be used for our applica-
tion: R3Au or RAuL compounds. The RAuL complexes
were preferred for their higher stability than R3Au [7,8].
The major improvement in the field was the preparation
of mono and polyfluoro aryl gold compounds, especially
neutral complexes of the ‘‘ArFAuL’’ [9] type. Many
reports in the literature concern fluorinated derivatives
such as 2,4,6-tris(trifluoromethyl)phenylgold(I) complexes
[8,10–13] with various ligands like triphenylarsine or
diphosphines for examples. The presence of a ‘‘ArF’’
fluoroaryl group provides greater stability compared to
aryl analogs. But as part of our study, fluorine atoms
were not desirable in polymers.
Entry
1
RAuPPh3
Yield (%)
89
Mp (°C)
152–153
AuPPh3
AuPPh3
2
91
196–197
3
4
90
96
137–138
136–137
O
AuPPh3
AuPPh3
O
At the beginning of the eighties, some studies were
performed on more classical aryl groups like anisole
and as ligand, the triphenylphoshine. In 1980, van Ko-
ten et al. [14] prepared 2,6-dimethoxy- and 2,4,6-tri-
methoxy-phenyl(triphenylphosphine)gold(I) complexes
with classic organometallic synthesis. Then, the 2,6-
dimethoxyphenyl(triphenylphosphine)gold(I) complex
was fully characterized by X-ray diffraction analysis by
Riley and Davis [15].
5
6
85
96
140–141
148–149
F
AuPPh3
AuPPh3
F
F
7
88
132–133
For our purpose, we choose to prepare derivatives
analogs to aryl(triphenylphosphine)gold(I) complexes
because of their easy handling. We report here the syn-
thesis of new vinylphenyl(triphenylphosphine)gold(I)
derivatives that are very important compounds for the
preparation of new doped materials with gold (e.g. by
copolymerization). We have applied the same procedure
to the synthesis of other gold derivatives: [i.e.
2,4,6-tris(trimethyl)- [16–18], 4-(methoxy)-, 3-methoxy,
4-fluoro-, 3-fluoro-, 3,5-difluoro-phenyl(triphenylphos-
phine)gold(I)]. All these derivatives are characterized
by 1H, 13C, 31P, 19F NMR, melting point determination,
and X-ray diffraction analysis. There is experimental evi-
dence of aurophilic Au(I)ꢀ ꢀ ꢀAu(I) [19–23] attraction
from crystallography.
AuPPh3
F
8
9
89
89
156–157
156–157
AuPPh3
AuPPh3
A series of gold complexes of the general type
[AuR(PPh3)] (Fig. 1) were prepared by standard meth-
ods in high yields (Table 1).
These derivatives were prepared by classical organo-
metallic synthesis under inert atmospheres. They were
isolated by standard methods and purified by crystalli-
zation in chloroform. It is important to note that all
these derivatives were air and water stable. In a matter
of fact, this stability allowed to study the vinyl substi-
tuted gold(I) complexes in different polymerization pro-
cedures. We can note that for these gold(I) complexes
the melting point is close to the temperature of decom-
position. For example the differential scanning calori-
metry (DSC) of complex 6 shows a melting point of
ca. 149 °C and a temperature of beginning decomposi-
tion of ca. 160 °C.
1) THF, -78 ˚C
RM
+
ClAuPPh3
RAuPPh3
2) 12 h, rt
M = Li; R = 4-CH2=CHPh (1), 3-CH2=CHPh (8), 2-CH2=CHPh (9)
M = MgBr; R = mesityl (2), 4-MeOPh (3), 3-MeOPh (4),
4-FPh (5), 3-FPh (6), 3,5-F2Ph (7)
Fig. 1. Sythesis of RAuPPh3 with RM reagents.

C. Croix et al. / Journal of Organometallic Chemistry 690 (2005) 4835–4843
4837
All these complexes were characterized by complete
NMR analysis. The 13C NMR spectra of complexes 1,
2, 4, 6, 7 and 8 were specific: a doublet (Fig. 2), was ob-
served for the carbon that was attached to the gold
atom. There was coupling between the ipso-carbon and
the phosphorus. This coupling was very extensive
(approximately 110 Hz) and has rarely been reported
in the literature [24,25]. This ipso-carbon was not ob-
served in complexes 3 and 5. To establish this coupling,
it was necessary that the CDCl3 solution in the NMR
tube must be very concentrated (in the range of 100 to
120 mg of complex).
In order to confirm the structures of these complexes,
an X-ray diffraction analysis was performed to deter-
mine their molecular structure. Crystal data and refine-
ment details for major complexes are presented in Table
8. Figs. 3–8 show the molecular structure of 1, 2, 3, 4, 6
and 7, respectively, with selected bond lengths and an-
gles in Tables 2–7. Complex 5 could not be analyzed be-
cause it was not a monocrystal.
Auꢀ ꢀ ꢀAu distance, respectively, of 3.135, 3.120 and
˚
3.108 A. These distances are in conformity with direct
aurophilic interaction: Auꢀ ꢀ ꢀAu separations must be less
˚
than 3.6 A [20,21].
Tables 2–7 summarize selected bond lengths and an-
gles for complexes 1, 2, 3, 4, 6 and 7.
We initially compared dimeric compounds. In com-
plexes 3, 6 and 7, Au–C bond lengths were between
˚
2.049(5) and 2.118(5) A, thus essentially equal and sim-
ilar to related distances in other arylgold complexes
[9,15]. These bond lengths were substantially shorter
than the predicted single bond length of approximately
˚
˚
˚
2.44 A (rAu = 1.34 A, rP = 1.10 A) and may indicate
some degree of Au(dp) ! P(dp) back bonding in these
linear complexes [26]. In the case of dimers, it was inter-
esting to note that the two Au–C distances in each com-
plex were very homogeneous and similar. These Au–C
bond lengths were a little longer than in ethynyl gold(I)
complexes [27] which Au–C bond lengths are in the
˚
range 1.983(8)–2.03(2) A.
All the complexes proved to have molecular struc-
tures that we have expected; however, some differences
were observed. Molecular structures of complexes 1, 2,
and 4 were confirmed by X-ray diffraction analysis and
these three complexes were monomers.
Comparison of NMR and X-ray diffraction analysis
revealed that as complexes were close to linearity, there
is coupling by bonds in 13C NMR and not spatial cou-
pling as previously supposed.
A classical synthesis method was used to prepare sta-
ble new vinylphenyl(triphenylphosphine)gold(I) com-
plexes. We report the synthesis of gold(I) complexes
Studies of X-ray diffraction of complexes 3, 6 and 7
(Figs. 5, 7 and 8; Tables 4, 6 and 7) reveals that the
Fig. 2. 13C NMR spectrum of complex 1. To establish this coupling by 13C NMR, the CDCl3 solution in the NMR tube must be very concentrated
(100 to 120 mg of the complex to reveal this small doublet).

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C. Croix et al. / Journal of Organometallic Chemistry 690 (2005) 4835–4843
Fig. 3. ORTEP view of complex 1. Displacement parameter ellipsoids
are drawn at the 50% probability level. H atoms are omitted for clarity.
Fig. 6. ORTEP view of complex 4. Displacement parameter ellipsoids
are drawn at the 50% probability level. H atoms are omitted for clarity.
Fig. 4. ORTEP view of complex 2. Displacement parameter ellipsoids
are drawn at the 50% probability level. H atoms are omitted for clarity.
Fig. 7. ORTEP view of complex 6. Displacement parameter ellipsoids
are drawn at the 50% probability level. H atoms are omitted for clarity.
with good overall yields from commercially available
chloro(triphenylphosphine)gold(I). 13C NMR spectra
properties for complexes 1, 2, 4, 6, 7 and 8 had particu-
lar features, with a large coupling constant between the
ipso-carbon and the phosphorous atom. However, in
complexes 3 and 5 the ipso-carbon could not be identi-
fied. The structures of 1, 2 and 4 were also confirmed
by X-ray crystal structure determination. On the other
hand, the complexes 3, 6 and 7 were dimeric. The radical
polymerization of the three vinylphenyl(triphenylphos-
phine)gold(I) (1, 8 and 9) are in progress and prelimin-
ary results are very promising for the application. The
synthesis of various complexes with other ligands like
triethylphosphine is also in progress in order to increase
reactivity toward polymerization.
Fig. 5. ORTEP view of complex 3. Displacement parameter ellipsoids
are drawn at the 50% probability level. H atoms are omitted for clarity.

C. Croix et al. / Journal of Organometallic Chemistry 690 (2005) 4835–4843
4839
Table 3
Selected bond lengths (A) and angles (°) for complex 2
˚
˚
Bond lengths (A)
Au(1)–P(1)
Au(1)–C(1)
C(1)–C(2)
C(1)–C(6)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
2.2891(12)
2.061(5)
1.404(7)
1.397(7)
1.390(7)
1.367(8)
1.391(9)
1.397(7)
Bond angles (°)
P(1)–Au(1)–C(1)
C(2)–C(1)–Au(1)
C(6)–C(1)–Au(1)
C(2)–C(1)–C(6)
C(1)–C(2)–C(3)
C(4)–C(3)–C(2)
C(3)–C(4)–C(5)
C(6)–C(5)–C(4)
C(1)–C(6)–C(5)
171.08(14)
118.9(3)
123.0(4)
117.9(5)
120.5(5)
122.0(6)
117.8(5)
121.8(5)
120.0(5)
Fig. 8. ORTEP view of complex 7. Displacement parameter ellipsoids
are drawn at the 50% probability level. H atoms are omitted for clarity.
Table 2
˚
Selected bond lengths (A) and angles (°) for complex 1
˚
Bond lengths (A)
Table 4
Au(1)–P(1)
Au(1)–C(1)
C(1)–C(2)
C(1)–C(6)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
2.2937(11)
2.046(4)
1.384(6)
1.393(6)
1.390(7)
1.374(6)
1.394(6)
1.381(6)
˚
Selected bond lengths (A) and angles (°) for complex 3
˚
Bond lengths (A)
Au(1)–P(1)
Au(1)–C(1)
Au(1)–Au(2)
Au(2)–P(2)
Au(2)–C(26)
C(1)–C(2)
C(1)–C(6)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
2.2953(19)
2.100(7)
3.1352(4)
2.299(2)
2.063(8)
1.289(11)
1.363(11)
1.375(12)
1.352(13)
1.396(13)
1.385(12)
1.372(11)
1.393(11)
1.394(12)
1.356(12)
1.378(12)
1.367(13)
Bond angles (°)
P(1)–Au(1)–C(1)
C(2)–C(1)–Au(1)
C(6)–C(1)–Au(1)
C(2)–C(1)–C(6)
C(1)–C(2)–C(3)
C(4)–C(3)–C(2)
C(3)–C(4)–C(5)
C(6)–C(5)–C(4)
C(1)–C(6)–C(5)
173.53(12)
122.0(3)
122.3(3)
115.1(4)
123.0(4)
121.2(4)
116.8(4)
121.3(4)
122.6(4)
C(5)–C(6)
C(26)–C(31)
C(26)–C(27)
C(27)–C(28)
C(28)–C(29)
C(29)–C(30)
C(30)–C(31)
Bond angles (°)
P(1)–Au(1)–C(1)
C(1)–Au(1)–Au(2)
P(1)–Au(1)–Au(2)
P(2)–Au(2)–C(26)
C(26)–Au(2)–Au(1)
P(2)–Au(2)–Au(1)
C(2)–C(1)–C(6)
C(1)–C(2)–C(3)
C(4)–C(3)–C(2)
C(3)–C(4)–C(5)
C(6)–C(5)–C(4)
173.1(2)
2. Experimental
88.94(19)
96.46(19)
177.2(2)
80.4(2)
2.1. Instrumentation, materials and reagents
102.29(5)
116.7(8)
125.6(9)
118.2(9)
119.3(8)
117.8(8)
122.4(9)
114.8(8)
122.8(8)
119.8(9)
118.6(9)
120.6(8)
123.3(9)
All reactions were carried out using standard Schlenk
techniques under an inert atmosphere (Ar). 1H
(200 MHz), 13C (50 MHz), 31P (81 MHz), 19F
(188 MHz) NMR spectra were recorded in CDCl3 on
a Bruker AC 200. The findings were as follows (in or-
der): chemical shift (d in ppm), multiplicity (s, d, t, m
for singlet, doublet, triplet, multiplet, respectively) and
coupling constant (J in Hz). ClAuPPh3, 4-bromosty-
rene, n-butyllithium, mesitylmagnesium bromide,
4-methoxyphenylmagnesium bromide, 4-fluoromagne-
sium bromide, 3-methoxyphenylmagnesium bromide,
C(1)–C(6)–C(5)
C(31)–C(26)–C(27)
C(28)–C(27)–C(26)
C(29)–C(28)–C(27)
C(28)–C(29)–C(30)
C(31)–C(30)–C(29)
C(30)–C(31)–C(26)

4840
C. Croix et al. / Journal of Organometallic Chemistry 690 (2005) 4835–4843
Table 5
Table 7
˚
˚
Selected bond lengths (A) and angles (°) for complex 4
Selected bond lengths (A) and angles (°) for complex 7
˚
Bond lengths (A)
˚
Bond lengths (A)
Au(1)–P(1)
Au(1)–C(1)
C(1)–C(2)
C(1)–C(6)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
2.2956(8)
2.056(3)
1.362(5)
1.401(5)
1.400(6)
1.376(6)
1.362(6)
1.391(5)
Au(1)–P(1)
Au(1)–C(25)
Au(1)–Au(2)
Au(2)–P(2)
Au(2)–C(1)
C(1)–C(2)
C(1)–C(6)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
2.2957(14)
2.111(5)
3.1080(3)
2.2988(13)
2.118(5)
1.184(8)
1.437(8)
1.472(9)
1.345(9)
1.378(10)
1.378(9)
1.334(8)
1.364(8)
1.362(9)
1.366(10)
1.352(10)
1.364(9)
Bond angles (°)
P(1)–Au(1)–C(1)
C(2)–C(1)–Au(1)
C(6)–C(1)–Au(1)
C(2)–C(1)–C(6)
C(1)–C(2)–C(3)
C(4)–C(3)–C(2)
C(3)–C(4)–C(5)
C(6)–C(5)–C(4)
C(1)–C(6)–C(5)
175.51(10)
123.0(3)
118.7(3)
118.2(3)
120.8(4)
120.6(4)
119.1(4)
120.7(4)
120.5(4)
C(5)–C(6)
C(25)–C(26)
C(25)–C(30)
C(26)–C(27)
C(27)–C(28)
C(28)–C(29)
C(29)–C(30)
Bond angles (°)
P(1)–Au(1)–C(25)
C(25)–Au(1)–Au(2)
P(1)–Au(1)–Au(2)
P(2)–Au(2)–C(1)
C(1)–Au(2)–Au(1)
P(2)–Au(2)–Au(1)
C(2)–C(1)–C(6)
C(1)–C(2)–C(3)
C(4)–C(3)–C(2)
C(3)–C(4)–C(5)
C(6)–C(5)–C(4)
172.52(15)
79.98(14)
105.55(4)
173.99(14)
85.87(12)
99.57(3)
121.6(5)
121.3(5)
121.7(6)
114.7(6)
123.5(6)
117.1(6)
120.5(5)
118.8(6)
123.5(7)
115.4(6)
123.0(6)
118.8(6)
Table 6
˚
Selected bond lengths (A) and angles (°) for complex 6
˚
Bond lengths (A)
Au(1)–P(1)
Au(1)–C(19)
Au(1)–Au(2)
Au(2)–P(2)
Au(2)–C(43)
C(19)–C(20)
C(19)–C(24)
C(20)–C(21)
C(21)–C(22)
C(22)–C(23)
C(23)–C(24)
C(43)–C(48)
C(43)–C(44)
C(44)–C(45)
C(45)–C(46)
C(46)–C(47)
C(47)–C(48)
2.2963(14)
2.049(5)
3.1203(3)
2.3085(13)
2.057(5)
1.368(8)
1.403(9)
1.504(14)
1.444(19)
1.24(2)
C(5)–C(6)–C(1)
C(26)–C(25)–C(30)
C(25)–C(26)–C(27)
C(26)–C(27)–C(28)
C(29)–C(28)–C(27)
C(28)–C(29)–C(30)
C(25)–C(30)–C(29)
1.72(2)
1.386(7)
1.400(8)
1.396(10)
1.378(12)
1.407(12)
1.510(11)
3-fluoromagnesium bromide, 3,5-difluoromagnesium
bromide and all solvents were all purchased from
Aldrich.
Bond angles (°)
2.2. General procedure with M = Li
P(1)–Au(1)–C(19)
C(19)–Au(1)–Au(2)
P(1)–Au(1)–Au(2)
P(2)–Au(2)–C(43)
C(43)–Au(2)–Au(1)
P(2)–Au(2)–Au(1)
C(20)–C(19)–C(24)
C(19)–C(20)–C(21)
C(22)–C(21)–C(20)
C(23)–C(22)–C(21)
C(22)–C(23)–C(24)
C(19)–C(24)–C(23)
C(48)–C(43)–C(44)
C(45)–C(44)–C(43)
C(46)–C(45)–C(44)
C(45)–C(46)–C(47)
C(46)–C(47)–C(48)
C(43)–C(48)–C(47)
173.41(17)
80.29(15)
104.68(3)
173.62(15)
86.57(13)
98.27(3)
116.3(6)
113.5(7)
113.3(9)
156(2)
82.2(19)
138.4(9)
116.2(5)
117.8(6)
124.6(6)
124.2(8)
107.8(9)
129.4(6)
To a solution of 4-bromostyrene (0.18 g, 1 mmol) in
THF (2 mL), 0.4 mL of n-BuLi 2.5 M (1 mmol) was
added dropwise at ꢁ78 °C. The mixture was stirred
for 10 min, and a solution of ClAuPPh3 (0.5 g,
1 mmol) in THF (15 mL) was added to the ‘‘para-
vinyl(phenyl)lithium’’. The mixture was allowed to
warm to room temperature, and mixed for 16 h. The
mixture was treated with a saturated solution of
ammonium chloride and extracted with diethylether.
The organic layers were washed with a saturated solu-
tion of sodium chloride. The organic layers were dried
over magnesium sulphate; and solvents were removed
under reduced pressure. The crude product was ob-
tained as a lightly yellow powder throught removal

C. Croix et al. / Journal of Organometallic Chemistry 690 (2005) 4835–4843
4841
of the solvent in vacuo. 1–9 were obtained as white
crystals via crystallization from CHCl3.
2.3.2. p-Methoxyphenyl(triphenylphosphine)Au(I) (3)
Yield: 90%, m.p.: 137–138 °C.1H NMR d ppm
(CDCl3, 200 MHz): 3.82 (3H, s), 6.95 (2H, d), 7.47–
7.68 (17 Har, m); 13C NMR d ppm (CDCl3, 50 MHz):
55.0 (1C), 113.5 (2C), 129.0 (6C, JC–P = 10.7 Hz),
130.9 (3C, JP–C = 49.7 Hz), 131.1 (3C, JC–P = 2.0 Hz),
134.3 (6C, JP–C = 13.7 Hz), 139.9 (2C), 157.8 (1C); 31P
NMR d ppm (CDCl3, 81 MHz): 45.
2.2.1. p-Vinylphenyl(triphenylphosphine)Au(I) (1)
Yield: 89% (0.5 g), m.p.: 152–153 °C. 1H NMR d ppm
(CDCl3, 200 MHz): 5.15 (1H, d, J = 10.8 Hz), 5.73 (1H,
d, J = 17.6 Hz), 6.73 (1H, dd, J = 10.9 Hz, J = 17.6 Hz),
7.47–7.76 (19 Har, m); 13C NMR d ppm (CDCl3,
50 MHz): 111.6 (1C), 125.2 (1C, d, JC–P = 5.2 Hz), 129
(6C, d, JC–P = 10.7 Hz), 131 (3C, d, JC–P = 49 Hz), 131.1
(3C, d, JC–P = 5.3 Hz), 134.3 (6C, JC–P = 13.7 Hz), 134.9
2.3.3. m-Methoxyphenyl(triphenylphosphine)Au(I) (4)
Yield: 96%, m.p.: 136–137 °C.1H NMR dppm (CDCl3,
200 MHz): 3.85 (3H, s) 6.74 (1H, m), 7.20 (3H, m), 7.47–
7.70 (15 Har, m); 13C NMR d ppm (CDCl3, 50 MHz): 55.0
(1C), 111.9 (1C), 124.1 (1C), 128.0 (1C), 129.0 (6C,
(1C), 137.8 (1C), 139.5 (1C), 172.6 (1C, d, JC–P
116 Hz); 31P NMR d ppm (CDCl3, 81 MHz): 45.
=
1
JC–P = 10.7 Hz), 130.9 (3C, JC–P = 48.4 Hz), 131.1
2.2.2. m-Vinylphenyl(triphenylphosphine)Au(I) (8)
Yield: 89% (0.5 g), m.p.: 156–157 °C. 1H NMR d ppm
(CDCl3, 200 MHz): 5.19 (1H, d, J = 10.9 Hz), 5.76 (1H,
d, J = 17.6 Hz), 6.76 (1H, dd, J = 10.9 Hz, J = 17.6 Hz),
7.24–7.70 (19 Har, m); 13C NMR d ppm (CDCl3,
50 MHz): 112.0 (1C), 123.7 (1C), 127.4 (1C), 129.0
(3C), 134.3 (6C, JP–C = 13.6 Hz), 158.7 (1C), 173.2 (1C,
JC–P = 115.9 Hz); 31P NMR d ppm (CDCl3, 81 MHz): 45.
2.3.4. p-Fluorophenyl(triphenylphosphine)Au(I) (5)
Yield: 85%, m.p.: 140–141 °C.1H NMR d ppm
(CDCl3, 200 MHz): 7.03 (2H, m), 7.47–7.73 (17 Har,
m); 13C NMR d ppm (CDCl3, 50 MHz): 114.1 (2C,
JC–F = 17.7 Hz), 129.0 (6C, JC–P = 10.8 Hz), 131.3
(6C, d, JC–P = 10.9 Hz), 131.2 (3C), 134.3 (6C, JC–P
=
13.6 Hz), 136.1 (1C), 137.5 (1C), 138.4 (1C), 139.2
(1C), 171.9 (1C, d, JC–P = 112.9 Hz); 31P NMR d ppm
(CDCl3, 81 MHz): 45.
(3C), 134.3 (6C, JP–C = 13.6 Hz), 140.1 (2C, JC–F
=
5.4 Hz), 161.6 (1C, JC–F = 241.2 Hz), 31P NMR d ppm
(CDCl3, 81 MHz): 45;19F NMR d ppm (CDCl3,
188 MHz): ꢁ119.40 (m, 1F).
2.2.3. o-Vinylphenyl(triphenylphosphine)Au(I) (9) [28]
Yield: 89% (0.5 g), m.p.: 156–157 °C.1H NMR d
ppm (CDCl3, 200 MHz): 5.20 (1H, d, J = 10.8 Hz),
5.82 (1H, d, J = 17.5 Hz), 7.16–7.48 (2H, m), 7.47–
2.3.5. m-Fluorophenyl(triphenylphosphine)Au(I) (6)
Yield: 96%, m.p.: 148–149 °C.1H NMR d ppm
(CDCl3, 200 MHz): 6.81 (1H, m), 7.36–7.68 (18 Har,
m); 13C NMR d ppm (CDCl3, 50 MHz): 112.3 (1C,
JC–F = 20.7 Hz), 125.2 (1C, JC–F = 15.0 Hz), 128.3
(1C), 129.1 (6C, JC–P = 10.7 Hz), 130.2 (3C), 131.2
(3C), 134.3 (6C, JP–C = 13.6 Hz), 134.9 (1C), 162.8
(1C, JC–F = 246.5 Hz), 174.5 (1C, JC–P = 115.2 Hz);
31P NMR d ppm (CDCl3, 81 MHz): 45; 19F NMR d
ppm (CDCl3, 188 MHz): ꢁ118.43 (m, 1F).
7.70 (18 Har, m); 13C NMR
d ppm (CDCl3,
50 MHz): 110.8 (1C), 124.4 (1C), 125.6 (1C), 126.4
(1C), 129.0 (6C, d, JC–P = 10.9 Hz), 131.2 (3C), 134.2
(6C, JC–P = 13.7 Hz), 139.6 (1C), 137.5 (1C), 143.8
(1C), 139.2 (1C), 146.1 (1C); 31P NMR d ppm
(CDCl3, 81 MHz): 45.
2.3. General procedure with M = MgBr
The appropriate organomagnesium bromide deriva-
tives (1 mmol) were added dropwise to a solution of
ClAuPPh3 (0.5 g, 1 mmol) in THF (15 mL) at ꢁ78 °C.
The mixture was allowed to warm to room temperature
and was mixed for 16 h. Treatment was the same as for
compound 1.
2.3.6. 3,5-Difluorophenyl(triphenylphosphine)Au(I) (7)
Yield: 88%, m.p.: 132–133 °C.1H NMR d ppm
(CDCl3, 200 MHz): 6.55 (1H, m), 7.14 (2H, m), 7.46–
7.65 (15 Har, m); 13C NMR d ppm (CDCl3, 50 MHz):
100.7 (1C, JC–F = 25.1 Hz), 120.6 (2C, JC–F = 12.0 Hz),
1
129.1 (6C, JC–P = 10.8 Hz), 130.5 (3C, JC–P
=
50.6 Hz), 131.3 (3C), 134.3 (6C, JP–C = 13.6 Hz), 162.6
(1C, JC–F = 249.4 Hz), 176.1 (1C, JC–P = 117.7 Hz), 31P
NMR d ppm (CDCl3, 81 MHz): 44; 19F NMR d ppm
(CDCl3, 188 MHz): ꢁ116.8 (m, 1F).
2.3.1. 2,4,6-Trimethylphenyl(triphenylphosphine)Au(I)
(2)
Yield: 91%, m.p.: 196–197 °C.1H NMR d ppm (CDCl3,
200 MHz): 2.27 (3H, s), 2.66 (6H, s), 6.98 (2H, s), 7.49–
7.71 (15 Har, m); 13C NMR d ppm (CDCl3, 50 MHz):
21.1 (1C), 26.8 (2C), 126.3 (2C, d, JC–P = 6.6 Hz), 129
(6C, JC–P = 10.6 Hz), 130.8 (3C, JC–P = 2.2 Hz), 131.3
(3C, JP–C = 48.2 Hz), 134.3 (6C, JP–C = 13.8 Hz), 135.0
(1C), 145.7 (1C), 169.8 (1C, JP–C = 111.1 Hz); 31P NMR
d ppm (CDCl3, 81 MHz): 46.
3. X-ray crystal structure determination
Suitable single crystals of 1, 2, 3, 4, 6 and 7 were
mounted on a glass fiber. Data collections were carried

4842
C. Croix et al. / Journal of Organometallic Chemistry 690 (2005) 4835–4843
Table 8
Crystal and refinement data for complexes 1, 2, 3, 4, 6, and 7
Compound
1
2
3
4
6
7
Formula
C26H22AuP
562.37
Triclinic
C27H26AuP
578.41
Monoclinic
P21/c
9.0251(1)
14.3916(2)
17.8986(3)
C50H44Au2P2O2
1132.72
Monoclinic
P21/c
13.5515(3)
11.9963(2)
26.9017(7)
C25H22AuOP
566.36
Triclinic
C48H38Au2F2P2
1108.66
Monoclinic
P21/c
13.6700(2)
11.6510(2)
25.8010(6)
C48H36Au2F4P2
1144.64
Monoclinic
P21/c
13.7647(2)
11.7638(2)
25.6862(6)
Formula weight
Crystal system
Space group
ꢀ
ꢀ
P1
P1
˚
a (A)
9.3850(4)
9.6898(6)
12.9710(8)
75.959(3)
70.290(3)
86.859(4)
1076.83(10)
2
8.8659(4)
10.7086(3)
12.7905(6)
72.921(3)
71.059(2)
80.279(3)
1094.32(8)
2
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
91.9775(6)
101.6633(7)
97.6010(7)
98.2129(6)
3
˚
V (A )
2323.48(6)
4
1.654
6.411
1128
4283.16(16)
4
1.757
6.956
2192
4073.20(11)
4
1.808
7.316
2128
4116.71(10)
4
1.847
7.249
2192
Z
qcalc. (g/cm3)
1.734
9.913
544
1.719
6.807
548
l (mmꢁ1
F(000)
)
h Range (°)
2.17; 28.59
12278
5227
1.82; 28.57
32711
5802
1.55; 28.52
51125
10565
2.97; 28.79
22242
5434
2.37; 28.67
52495
9978
2.35; 28.69
47878
10338
Reflections collected
Independent reflections
Rint
0.039
0.053
0.096
0.046
0.081
0.085
Maximum/minimum transmission
R1 [I > 2r(I)]
wR2 (all data)
0.419/0.518
0.0313
0.0701
0.250/0.294
0.0275
0.0983
0.348/0.516
0.0495
0.1188
0.208/0.279
0.0253
0.0613
0.134/0.271
0.0351
0.0909
0.366/0.701
0.0369
0.0869
out at room temperature on a Bruker-Nonius Kappa
CCD diffractometer equipped with graphite-monochro-
mated Mo (Ka) radiation (k = 0.71073 A). Cell parame-
iques du CEA Le Ripault’’ for recording NMR spectra,
and the ‘‘Laboratoire de Cristallochimie’’ of Marseille
University for X-ray diffraction analysis.
˚
ters were retrieved and refined using DENZO-SMN [29]
software on all reflections. Data reductions were per-
formed with the DENZO-SMN [29] software. An empirical
absorption correction based on the symmetry-equivalent
reflections was applied to each data set using the SORTAV
[30] program. The structure were solved either by SIR92
[31] or SHELXS-97 [32] and refined with the SHELXL-97 pro-
gram [33]. The hydrogen atoms were placed in geometri-
cally idealized positions and constrained to ride on their
parent atoms. Detailed crystal data are listed in Table 8.
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