Synthesis of highly stable intermediates in Michael-type additions to the double bond in (SPPh2)2C=CH2

Article abstract of DOI:10.1039/a703357e

Treatment of vinylidenebis(diphenylphosphine) with elemental sulfur under reflux led to vinylidenebis(diphenylphosphine) disulfide, (SPPh₂)₂C=CH₂, in good yields. Its co-ordination to a gold(III) centre activates the carbon-carbon double bond. Thus, the chelate complex [Au(C₆F₅)₂{(SPPh₂) ₂C=CH₂}]ClO₄ reacted rapidly with carbon- or oxygen-donor nucleophiles (Nu^-), such as acac^- (acetylacetonate), CN^-, C₅H₅^- or OEt^-, forming methanide-type derivatives [Au(C₆F₅)₂{(SPPh₂) ₂CCH₂Nu}]. These products can be considered as intermediates in Michael-type additions of HNu to the C=C bond, which in this particular case display high stabilities, allowing their isolation as solids. The crystal structure of the cyclopentadienyl derivative has been established by X-ray crystallography and displays a square-planar gold(III) centre with a cis disposition of the pentafluorophenyl groups and sulfur atoms of the chelating ligand, and sp² hybridization of the endocyclic carbon atom with partial P-C double-bond character.

Full text of DOI:10.1039/a703357e

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Synthesis of highly stable intermediates in Michael-type additions to
the double bond in (SPPh ) C᎐CH
᎐
2 2
2
Eduardo J. Fernández,a M. Concepción Gimeno,b Peter G. Jones,c Antonio Laguna,*,b
José M. López-de-Luzuriaga a and Elena Olmosa
a
Departamento de Química, Universidad de La Rioja, Obispo Bustamante 3, E-26001 Logroño,
Spain
b Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón,
Universidad de Zaragoza-CSIC, E-50009 Zaragoza, Spain
c Institüt für Anorganische und Analytische Chemie der Technischen Universität, Postfach 3329,
D-38023 Braunschweig, Germany
Treatment of vinylidenebis(diphenylphosphine) with elemental sulfur under reflux led to
vinylidenebis(diphenylphosphine) disulfide, (SPPh ) C᎐CH , in good yields. Its co-ordination to a gold() centre
᎐
2
2
2
activates the carbon–carbon double bond. Thus, the chelate complex [Au(C F ) {(SPPh ) C᎐CH }]ClO reacted
᎐
6
5
2
2
2
2
4
rapidly with carbon- or oxygen-donor nucleophiles (NuϪ), such as acacϪ (acetylacetonate), CNϪ, C5H5Ϫ or OEtϪ,
forming methanide-type derivatives [Au(C6F5)2{(SPPh2)2CCH2Nu}]. These products can be considered as
intermediates in Michael-type additions of HNu to the C᎐C bond, which in this particular case display high
᎐
stabilities, allowing their isolation as solids. The crystal structure of the cyclopentadienyl derivative has been
established by X-ray crystallography and displays a square-planar gold() centre with a cis disposition of the
pentafluorophenyl groups and sulfur atoms of the chelating ligand, and sp2 hybridization of the endocyclic carbon
atom with partial P᎐C double-bond character.
The co-ordination chemistry of vinylidenebis(diphenyl-
+
Ph2
P
phosphine)1–4 and the reactivity of its carbon–carbon double
bond in addition reactions have been studied in the last decade.
In the course of these investigations it has been shown that,
although the double bond in unco-ordinated vinylidenebis-
(diphenylphosphine) is scarcely susceptible to nucleophilic
attack, except under extreme reaction conditions,4–6 complex-
ation to a metal centre2a,3,4,7,8 or quaternization of the phos-
phorus atoms9 activates the double bond in such a manner that
various nucleophiles can be added through Michael-type reac-
tions. In these processes the species HNu is added to complexes
Ph2
P
R
R
R
R
+ Nu–
Au
Au
C
H
CH2
– HNu
P
Ph2
P
Ph2
Ph2
P
R
R
Ph2
P
+ Nu–
– Cl –
Au
R
Au
C
CH2Nu
Cl
Ph2P
C
CH2
P
Ph2
R
[M]᎐(PPh ) C᎐CH
to give the products [M]᎐(PPh2)2-
᎐
2
2
2
CHCH2Nu, where the first step is always the attack of the
nucleophile NuϪ on the C atom of the C᎐C bond. However,
Scheme 1 R = C6F5
᎐
β
the product formed in the first step had not been isolated.
for completion of the addition to the double bond, because the
electrophile gold() is present in the same molecule as the car-
banion; thus a similar process to that described for the Ph2P-
(S)CH2(S)PPh2 derivative could be expected. Surprisingly, the
products isolated in these reactions are always those formed in
the first step, containing a six-membered ring and displaying
both carbanion and electrophile together in the same molecule
without any interaction between them (see Scheme 2). This fact
reveals that these particular intermediates are not only isolable,
but also even more stable than expected.
We have recently reported that the reaction of [Au(C6F5)2-
Cl{PPh C(᎐CH )PPh }] with nucleophilic agents NuϪ allows
᎐
2
2
2
the isolation of these intermediates, affording methanide-like
derivatives [Au(C6F5)2{(PPh2)2CCH2Nu}].10 These complexes
are structurally and electronically similar to the bis(diphenyl-
phosphino)methanide derivative [Au(C6F5)2{(PPh2)2CH}],
which is formed by extraction of one proton from [Au(C6F5)2-
{(PPh2)2CH2}]ClO4 when treated with a nucleophile NuϪ
(HϪ); the excess electron density is delocalized over both
P᎐C bonds11 (Scheme 1).
In contrast, it has been reported that when the same reaction
is carried out with the bis(diphenylphosphino)methane
disulfide ligand the initially formed six-membered ring is rap-
idly transformed into a four-membered ring through the
co-ordination of the methanide carbon to the gold() centre12
(see Scheme 2), and this can be considered as electrophilic
attack of the gold() centre on the unsaturated carbon.
In order to investigate the stability of the intermediates in a
Michael addition to vinylidenebis(diphenylphosphine) disulfide
we have synthesized the chelate bis(pentafluorophenyl) complex
Results and Discussion
When vinylidenebis(diphenylphosphine) disulfide is treated
with [{Au(C6F5)2(µ᎐Cl)}2] in a 2:1 molar ratio one of the sulfur
atoms co-ordinates to the gold centre, rupturing the chlorine
bridges to give the monodentate [Au(C6F5)2Cl{SPPh2C-
(᎐CH )PPh ᎐S}] 1 (Scheme 3) as a white solid soluble in com-
᎐
᎐
2
2
mon organic solvents. It presents a cis disposition of the pen-
tafluorophenyl groups, as shown by its 19F NMR spectrum,
which shows two different types of C6F5 with relative intensities
1:1. Its infrared spectrum exhibits the ν(Au᎐Cl) stretching
[Au(C F ) {(SPPh ) C᎐CH }]ClO to study its reactivity with
᎐
6
5
2
2
2
2
4
nucleophiles NuϪ. These reactions provide optimum conditions
J. Chem. Soc., Dalton Trans., 1997, Pages 3515–3518
3515

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+
Ph2
P
Ph2
P
S
R
R
S
S
S
S
R
R
R
R
+ Nu–
Au
H
PPh2
S
Au
Au
CH2
C
H
– HNu
P
Ph2
C
P
Ph2
P
Ph2
+
Ph2
P
Ph2
P
S
R
R
S
S
S
R
R
R
R
+ Nu–
Au
PPh2
S
Au
Au
C
CH2
C
CH2Nu
S
P
C
P
Ph2
Ph2
NuH2C
P
Ph2
Scheme 2 R = C6F5
O
Ph2
Ph2
P
Ph2
P
S
S
P
R
R
O
S
S
R
N
S
S
R
R
Au
Au
Au
P
Ph2
R
P
Ph2
P
Ph2
4
3
5
(vii )
(iv)
(vi )
Ph2
Ph2
P
S
R
R
P
O
S
R
(viii )
Au
(v )
Au
C
CH2
ClO4
S
P
Ph2
R
S
P
Ph2
6
2
(iii )
(ii )
Ph2
P
Ph2
P
C
P
Ph2
S
(i )
S
R
CH2
C
CH2
Au
R
S
S
P
Ph2
Cl
1
Scheme 3 R = C6F5. (i) ½ [{Au(C6F5)2(µ-Cl)}2]; (ii) AgClO4; (iii) [Au(C6F5)2(OEt2)2]ClO4; (iv) Tl(acac); (v) [Au(C6F5)2(acac)]; (vi) KCN; (vii) TlC5H5;
(viii) NaOEt
band at 334 cmϪ1 and two ν(P᎐S) vibrations at 594 and 613
(QNu = KCN, TlC5H5 or NaOEt) results in the formation of the
corresponding QClO4 and addition of NuϪ to the exocyclic car-
bon centre to give [Au(C6F5)2{(SPPh2)2CCH2Nu}] (NuϪ = CNϪ
᎐
cmϪ1, corresponding to the single and double bond, respectively
(614 cmϪ1 for the free diphosphine disulfide).
Complex 1 reacts with an equimolecular amount of AgClO4
Ϫ
4, C5H5 5, or OEtϪ 6). Complexes 3–6 are air- and moisture-
to give [Au(C F ) {(SPPh ) C᎐CH }]ClO 2. The same product
can be prepared by a ligand-displacement reaction of [Au-
stable in the solid state and soluble in common organic solvents,
except hexane. Their IR spectra show a band in the region 569–
᎐
6
5
2
2
2
2
4
(C6F5)2(OEt2)2]ClO4 with (SPPh ) C᎐CH , as represented in
579 cmϪ1 [ν(P᎐S)], and also bands at 1505m, 967m, 804m and
᎐
᎐
2
2
2
Scheme 3. Compound 2 is obtained in good yields as a white
solid, soluble in chlorinated solvents and acetone and insoluble
in diethyl ether and hexane.
As mentioned above, the co-ordination of vinylidenebis-
(diphenylphosphine) extensively activates its double
bond 2a,3,4,7,8 and the same effect is observed here for vinyli-
denebis(diphenylphosphine) disulfide. This activation occurs in
such a manner that the nucleophilic addition in complex 2 takes
795m cmϪ1, due to the presence of C6F5 groups linked to a
gold() centre; the last two confirm the cis disposition.13
The presence of equivalent pentafluorophenyl groups is con-
firmed in the 19F NMR spectra (see Experimental section). The
addition of the nucleophile to the Cβ of the double bond leads to
the presence of an excess of electron density at the Cα atom,
which is delocalized through both P᎐C bonds. This is reflected in
the 31P-{1H} NMR spectra, in which the chemical shift for these
phosphorus decreases from δ 41.7 in complex 2 to δ 36.0–38.0
for 3–6. The breaking of the double bond also produces a change
in both chemical shift and pattern corresponding to the protons
of the CH2 group in their NMR spectra from an AAЈXXЈ spin
system at δ 7.15 to a triplet located between δ 2.66 and 3.47.
The structure of complex 5 has been established by X-ray
diffraction studies. The molecule is shown in Fig. 1 with
selected bond lengths and angles in Table 1. The gold() centre
has a planar geometry, being bonded to the two pentafluoro-
phenyl groups and chelated by the two sulfur atoms of the
diphosphine disulfide ligand. The major deviation of the angles
from the ideal 90Њ is positive and is observed within the chelate
ligand, S᎐Au᎐S 100.81(3)Њ, whereas the narrowest angles are
place only to the Cβ atom of the C᎐C bond, giving rise to
᎐
derivatives [Au(C6F5)2{(SPPh2)2CCH2Nu}], which can be con-
sidered as the products formed in the first step of a normal
Michael addition, displaying their striking high stability. Thus,
the reaction between equimolecular amounts of 2 and Tl(acac)
(acac = acetylacetonate) gives rise to the precipitation of
TlClO4 and addition of acetylacetonate to the Cβ atom, afford-
ing the neutral derivative [Au(C6F5)2{(SPPh2)2CCH2CH-
(COMe)2}] 3 (Scheme 3). This product can alternatively be
prepared by treating (SPPh ) C᎐CH with [Au(C6F5)2(acac)],
᎐
2
2
2
which contains the nucleophile.
Carbon- or oxygen-donor nucleophiles can be employed in
these reactions. Thus, treatment of complex 2 with QNu
3516
J. Chem. Soc., Dalton Trans., 1997, Pages 3515–3518

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photometer, over the range 4000–200 cmϪ1, using Nujol mulls
between polyethylene sheets, 1H, 19F and 31P NMR spectra on a
Bruker ARX 300 in CDCl3 solutions, chemical shifts being
quoted relative to SiMe4 (1H, external), CFCl3 (19F, external)
and H3PO4 (85%) (31P, external). The elemental analyses (C, H,
N, S) were performed with a Perkin-Elmer 2400 microanalyzer.
Mass spectra were recorded on a VG Autospec instrument
using FAB techniques and 3-nitrobenzyl alcohol as matrix. All
experiments were carried out at room temperature. The starting
materials (PPh ) C᎐CH ,15 (SPPh ) C᎐CH ,16 [{Au(C6F5)2-
᎐
᎐
2
2
2
2
2
2
(µ-Cl)}2]17 and [Au(C6F5)2(acac)]18 were prepared according
to the literature. The complex [Au(C6F5)2(OEt2)2]ClO4 was pre-
pared in situ by reaction of [{Au(C6F5)2(µ-Cl)}2] with 2 equiva-
lents of AgClO4 in diethyl ether.
Fig. 1 Structure of complex 5 in the crystal. Displacement parameter
ellipsoids represent 50% probability surfaces. Hydrogen atoms and
solvent are omitted for clarity
Syntheses
[Au(C F ) Cl{SPPh C(᎐CH )PPh ᎐S}] 1. To a dichlorometh-
᎐
᎐
2
6
5
2
2
2
ane solution (20 cm3) of [{Au(C6F5)2(µ-Cl)}2] (0.112 g, 0.1
mmol) was added (SPPh ) C᎐CH (0.092 g, 0.2 mmol). After
᎐
2
2
2
stirring for 4 h the solution was concentrated to ca. 5 cm3.
Addition of hexane led to complex 1 as a white solid (0.168 g,
82%) (Found: C, 44.0; H, 1.7; S, 6.35. Calc. for C38H22Au-
ClF10P2S2: C, 44.45; H, 2.15; S, 6.25%). 31P-{1H} NMR: δ 41.7 (s,
Table 1 Selected bond lengths (Å) and angles (Њ) for complex 5
Au᎐C(61)
Au᎐S(2)
2.032(3)
2.3552(9)
1.709(3)
1.813(4)
1.719(3)
1.811(3)
1.538(4)
1.312(6)
1.460(7)
1.455(6)
Au᎐C(51)
Au᎐S(1)
2.033(3)
2.3626(9)
1.807(3)
2.0459(11)
1.802(3)
2.0700(12)
1.494(5)
1.466(5)
1.307(7)
1P, Au᎐P᎐S) and 45.5 (s, 1P, P᎐S). 1H NMR: δ 6.89 (AAЈXXЈ, 2
P(1)᎐C(1)
P(1)᎐C(21)
P(2)᎐C(1)
P(2)᎐C(41)
C(1)᎐C(2)
C(3)᎐C(4)
C(4)᎐C(5)
C(6)᎐C(7)
P(1)᎐C(11)
P(1)᎐S(1)
P(2)᎐C(31)
P(2)᎐S(2)
C(2)᎐C(3)
C(3)᎐C(7)
C(5)᎐C(6)
᎐
H, CH2, N = 65.0 Hz). 19F NMR: δ Ϫ122.4 (m, o-F ), Ϫ153.6
(t, p-F, JF F = 20.0), Ϫ159.0 (m, m-F ), Ϫ122.6 (m, o-F ), Ϫ157.7
(t, p-F, JF F = 20.2 Hz) and Ϫ161.9 (m, m-F ). FAB mass
spectrum: m/z = 992 (88, [M Ϫ Cl]ϩ) and 658 (100%,
[Au{(SPPh ) C᎐CH }]ϩ).
᎐
2
2
2
[Au(C F ) {(SPPh ) C᎐CH }]ClO 2. Method (a). To
a
᎐
6
5
2
2
2
2
4
C(61)᎐Au᎐C(51)
C(51)᎐Au᎐S(2)
C(51)᎐Au᎐S(1)
C(1)᎐P(1)᎐C(11)
C(11)᎐P(1)᎐C(21) 107.4(2)
C(11)᎐P(1)᎐S(1)
C(1)᎐P(2)᎐C(31)
C(31)᎐P(2)᎐C(41) 107.3(2)
C(31)᎐P(2)᎐S(2)
P(1)᎐S(1)᎐Au
C(2)᎐C(1)᎐P(1)
P(1)᎐C(1)᎐P(2)
C(4)᎐C(3)᎐C(7)
C(7)᎐C(3)᎐C(2)
C(6)᎐C(5)᎐C(4)
C(6)᎐C(7)᎐C(3)
89.54(13)
173.75(10)
85.43(10)
107.5(2)
C(61)᎐Au᎐S(2)
C(61)᎐Au᎐S(1)
S(2)᎐Au᎐S(1)
C(1)᎐P(1)᎐C(21) 114.6(2)
C(1)᎐P(1)᎐S(1) 114.09(11)
C(21)᎐P(1)᎐S(1) 107.97(12)
C(1)᎐P(2)᎐C(41) 115.3(2)
C(1)᎐P(2)᎐S(2)
84.22(9)
174.97(9)
100.81(3)
freshly prepared solution of [Au(C6F5)2(OEt2)]ClO4 (0.2
mmol) in diethyl ether (20 cm3) was added (SPPh ) C᎐CH
᎐
2
2
2
(0.092 g, 0.2 mmol). After stirring for 3 h a white precipitate of
complex 2 was filtered off (0.205 g, 94%).
Method (b). A dichloromethane solution (20 cm3) of complex
1 (0.103 g, 0.1 mmol) was treated with AgClO4 (0.027 g, 0.1
mmol). After stirring for 3 h the AgCl formed was filtered off.
Concentration of the solution to ca. 5 cm3 and addition of
diethyl ether (20 cm3) gave complex 2 as a white solid (0.131 g,
60%) (Found: C, 41.65; H, 2.5; S, 5.95. Calc. for C38H22AuCl-
F10O4P2S2: C, 41.85; H, 2.05; S, 5.9%). 31P-{1H} NMR: δ 41.7
104.62(12)
109.2(2)
114.40(12)
103.70(11)
105.71(4)
119.3(2)
115.8(2)
107.0(4)
121.2(3)
107.7(4)
105.2(4)
C(41)᎐P(2)᎐S(2) 106.17(11)
P(2)᎐S(2)᎐Au
104.28(4)
120.4(2)
117.0(3)
131.7(4)
110.6(4)
109.4(4)
C(2)᎐C(1)᎐P(2)
C(3)᎐C(2)᎐C(1)
C(4)᎐C(3)᎐C(2)
C(3)᎐C(4)᎐C(5)
C(5)᎐C(6)᎐C(7)
1
(s). H NMR: δ 7.15 (AAЈXXЈ, 2 H, CH2, N = 69.2 Hz). 19F
NMR: δ Ϫ122.3 (m, o-F ), Ϫ153.7 (t, p-F, JF F = 20.0 Hz) and
Ϫ159.1 (m, m-F ). FAB mass spectrum: m/z = 992 (65, Mϩ)
and 658 (100%, [Au{(SPPh ) C᎐CH }]ϩ).
᎐
2
2
2
C᎐Au᎐S 85.43(10) and 84.22(9)Њ. The Au᎐C bond distances,
2.032(3) and 2.033(3) Å, are shorter than in other gold()
complexes with diphosphine ligands, probably as a consequence
of the higher trans influence of the phosphorus compared to
the sulfur ligands. The Au᎐S distances are 2.3552(9) and
2.3626(9) Å, similar to others in gold() derivatives with simi-
lar ligands, e.g. [Au(C6F5)2(SPPh2CHPPh2)] [2.345(2) Å].14 The
P(1)᎐C(1) and P(2)᎐C(1) bond lengths are 1.709(3) and 1.719(3)
Å, shorter than those found in complexes with the diphosphine,
[Au(C6F5)2{(SPPh2)2CCH2CH(COMe)2}] 3. Method (a). To
a dichloromethane solution (20 cm3) of complex 2 (0.218 g, 0.2
mmol) was added Tl(acac) (0.060 g, 0.2 mmol). The reaction
mixture was stirred under nitrogen for 3 h and the TlClO4
formed was then filtered off. The resulting solution was concen-
trated in a vacuum and the addition of hexane (15 cm3) led to
complex 3 as a yellow solid (0.120 g, 55%).
Method (b). To a solution of (SPPh ) C᎐CH (0.092 g, 0.2
᎐
2
2
2
mmol) in dichloromethane (20 cm3) was added [Au(C6F5)2-
(acac)] (0.126 g, 0.2 mmol). After 1 h of stirring under nitrogen
the solvent was evaporated and hexane was added to precipitate
complex 3 as a white solid (0.153 g, 70%) (Found: C, 47.75; H,
2.7; S, 5.5. Calc. for C43H29AuF10O2P2S2: C, 47.35; H, 2.7; S,
such as [{AuCl[PPh C(᎐CH )PPh ]} ] [1.828(6) and 1.833(6)
᎐
2
2
2
2
Å],4 or in other derivatives where a Michael addition has taken
place, such as [PdI2{(PPh2)2CHCH2OCH2CH2(3-SC4H3)}]
[1.84(2) and 1.90(1) Å].3d This indicates that the negative charge
of the methanide carbon is delocalized over the P᎐C bonds,
conferring on them a degree of multiple bonding. The
C(1)᎐C(2) distance, 1.538(4) Å, corresponds to a single bond.
The C᎐C distances within the cyclopentadienyl ring allow an
unambiguous assignment of single- and double-bond positions,
and there is no indication of disorder.
1
5.9%). 31P-{1H} NMR: δ 36.3 (s). H NMR: δ 1.26 (s, 6 H,
3
3
CH3), 2.66 (dt, 2 H, CH2, JH P = 21.5, JH H = 5.3 Hz) and 2.95
(t, 1 H, CH). 19F NMR: δ Ϫ121.9 (m, o-F ), Ϫ157.1 (t, p-F,
JF F = 20.0 Hz) and Ϫ161.4 (m, m-F ). FAB mass spectrum:
m/z = 1091 (53, Mϩ), 758 (82, [M Ϫ 2C6F5]ϩ) and 658 (100%
[Au{(SPPh ) C᎐CH }]ϩ).
᎐
2
2
2
[Au(C6F5)2{(SPPh2)2CCH2CN}] 4. To a suspension of com-
plex 2 (0.218 g, 0.2 mmol) in methanol (10 cm3) and under
nitrogen was added KCN (0.012 g, 0.2 mmol) and the mixture
was stirred for 2 h. Evaporation of the solvent to dryness and
Experimental
Instrumentation and materials
The IR spectra were recorded on a Perkin-Elmer 883 spectro-
J. Chem. Soc., Dalton Trans., 1997, Pages 3515–3518
3517

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NMR: δ Ϫ121.8 (m, o-F ), Ϫ157.3 (t, p-F, JF F = 19.9 Hz) and
Ϫ161.4 (m, m-F ). FAB mass spectrum: m/z = 991 (50,
Table 2 Details of data collection and structure refinement for
complex 5
[M Ϫ OEt]ϩ) and 658 (100%, [Au{(SPPh ) C᎐CH }]ϩ).
᎐
2
2
2
Chemical formula
M
C46H34AuF10P2S2
1099.76
Crystallography
Crystal habit
Crystal size/mm
Crystal system
Space group
a/Å
b/Å
c/Å
α/Њ
Irregular orange tablet
0.70 × 0.60 × 0.30
Triclinic
The crystal of complex 5 was mounted in inert oil on a glass
fibre. Data were collected using monochromated Mo-Kα radi-
ation (λ = 0.710 73 Å). Diffractometer type: Siemens P4
equipped with an LT-2 low-temperature attachment. Scan type
ω. Cell constants were refined from setting angles of 65 reflec-
tions in the range 2θ = 6–25Њ. Absorption corrections were
applied on the basis of ψ scans. The structure was solved by the
heavy-atom method and refined on F 2 (program SHELXL
93).19 The complex crystallizes with half a molecule of hexane
per asymmetric unit. All non-hydrogen atoms were refined
anisotropically, with the exception of the solvent carbon atoms.
Hydrogen atoms were included using a riding model. Further
details are given in Table 2.
¯
P1
11.617(2)
12.163(2)
16.005(2)
86.313(8)
75.125(10)
84.972(8)
2175.3(6)
2
1.679
1082
Ϫ100
55
β/Њ
γ/Њ
U/Å3
Z
Dc/Mg mϪ3
F(000)
T/ЊC
2θmax/Њ
CCDC reference number 186/635.
µ(Mo-Kα)/mmϪ1
Transmission factor range
No. reflections measured
No. unique reflections
Rint
3.627
0.625–1.0
12 427
9876
0.035
0.028
0.065
535
481
1.008
Acknowledgements
We thank the Dirección General de Investigación Científica
y Técnica (no. PB94-0079) and the Fonds der Chemischen
Industrie for financial support.
R a [F,F > 4σ(F)]
wR b (F 2, all reflections)
No. parameters
No. restraints
S c
References
Maximum ∆ρ/e ÅϪ3
0.91
1 P. A. Dolby, M. M. Harding, N. Newar and A. K. Smith, J. Chem.
Soc., Dalton Trans., 1992, 2939.
¹
a
2
R
(F ) = Σ Fo| Ϫ |Fc /Σ|Fo|. b wR (F 2) = [Σw(Fo2 Ϫ Fc )2/Σw(Fo2)2]²;
2
2 (a) G. R. Cooper, D. M. McEwan and B. L. Shaw, Inorg. Chim.
Acta, 1983, 76, L165; (b) G. R. Cooper, F. S. M. Hassan, B. L. Shaw
and M. Thornton-Pett, J. Chem. Soc., Chem. Commun., 1985, 614;
(c) G. R. Cooper, D. M. McEwan and B. L. Shaw, Inorg. Chim. Acta,
1986, 122, 207.
w
Ϫ1 = σ2(Fo2) ϩ (aP )2 ϩ bP, where P = (Fo2 ϩ 2Fc )/3 and a and b are
¹
constants adjusted by the program. c S = [Σw(Fo2 Ϫ Fc )2/(n Ϫ p)]², where
2
n is the number of data and p the number of parameters.
3 (a) F. S. M. Hassan, S. J. Higgins, G. B. Jacobsen, B. L. Shaw and
M. Thornton-Pett, J. Chem. Soc., Dalton Trans., 1988, 3011; (b) S. J.
Higgins and B. L. Shaw, J. Chem. Soc., Dalton Trans., 1989, 1527;
(c) A. M. Herring, S. J. Higgins, G. B. Jacobsen and B. L. Shaw,
J. Chem. Soc., Chem. Commun., 1986, 882; (d) G. King, S. J. Higgins
and A. Hopton, J. Chem. Soc., Dalton Trans., 1992, 3403.
4 H. Schmidbaur, R. Herr, G. Müller and J. Riede, Organometallics,
1985, 4, 1208.
5 J. L. Bookhan, W. McFarlane and J. Colquhoun, J. Chem. Soc.,
Chem. Commun., 1986, 1041; J. L. Bookhan, W. McFarlane and
M. Thornton-Pett, J. Chem. Soc., Dalton Trans., 1992, 2353.
6 H. Schmidbaur, R. Herr and J. Riede, Angew. Chem., Int. Ed. Engl.,
1984, 23, 247.
addition of diethyl ether led to precipitation of the KClO4
formed in the reaction, which was filtered off over Celite. The
solution was then concentrated in a vacuum to ca. 5 cm3 and
hexane (15 cm3) were added to precipitate complex 4 as a crys-
talline yellow solid (0.102 g, 50%) (Found: C, 46.55; H, 2.25; N,
1.2; S, 6.0. Calc. for C39H22AuF10NP2S2: C, 46.05; H, 2.2; N, 1.4;
1
S, 6.3%). 31P-{1H} NMR: δ 37.7 (s). H NMR: δ 2.76 (t, 2 H,
CH2, 3JH P = 19.2 Hz). 19F NMR: δ Ϫ121.9 (m, o-F ), Ϫ156.7 (t,
p-F, JF F = 20.0 Hz) and Ϫ161.1 (m, m-F ). FAB mass spec-
trum: m/z = 1019 (65, [M ϩ H]ϩ), 684 (100, [M Ϫ 2C6F5]ϩ) and
658 (55%, [Au{(SPPh ) C᎐CH }]ϩ).
᎐
2
2
2
7 F. S. M. Hassan, B. L. Shaw and M. Thornton-Pett, J. Chem. Soc.,
Dalton Trans., 1988, 89.
8 X. L. R. Fontaine, F. S. M. Hassan, S. J. Higgins, G. B. Jacobsen,
B. L. Shaw and M. Thornton-Pett, J. Chem. Soc., Chem. Commun.,
1985, 1635.
9 H. Schmidbaur, R. Herr, Th. Pollok, A. Schier, G. Müller and
J. Riede, Chem. Ber., 1985, 118, 3105.
10 E. J. Fernández, M. C. Gimeno, P. G. Jones, A. Laguna and
M. E. Olmos, Organometallics, 1997, 16, 1130.
11 R. Usón, A. Laguna, M. Laguna, B. R. Manzano, P. G. Jones and
G. M. Sheldrick, J. Chem. Soc., Dalton Trans., 1984, 839.
12 A. Laguna, M. Laguna, A. Rojo and M. N. Fraile, J. Organomet.
Chem., 1986, 315, 269.
13 R. Usón, A Laguna, J. García and M. Laguna, Inorg. Chim. Acta,
1979, 37, 201.
14 R. Usón, A. Laguna, M. Laguna, M. N. Fraile, P. G. Jones and
C. F. Erbrügger, J. Chem. Soc., Dalton Trans., 1989, 73.
15 I. J. Colquhoun and W. McFarlane, J. Chem. Soc., Dalton Trans.,
1982, 1915; H. Schmidbaur and Th. Pollok, Helv. Chim. Acta, 1984,
67, 2175.
16 H. Schmidbaur, R. Herr and G. Müller, Z. Chem., 1984, 24, 378.
17 R. Usón, A. Laguna, M. Laguna and J. A. Abad, J. Organomet.
Chem., 1983, 249, 437.
[Au(C6F5)2{(SPPh2)2CCH2(C5H5)}]ؒ0.5C6H14 5. To a dichloro-
methane solution (20 cm3) of complex 2 (0.218 g, 0.2 mmol)
under a nitrogen atmosphere was added TlC5H5 (0.054 g, 0.2
mmol). After stirring for 3 h the TlClO4 was filtered off and the
solution was concentrated to ca. 5 cm3. Addition of hexane led
to complex 5 as an orange solid (0.09 g, 41%) (Found: C, 50.05;
H, 3.15; S, 5.75. Calc. for C46H34AuF10P2S2: C, 50.25; H, 3.1; S,
1
5.85%). 31P-{1H} NMR: δ 36.0 (s). H NMR: δ 1.99 (s, 2 H,
3
CH᎐CCH CH᎐CH), 3.06 (t, 2 H, P CCH , J = 21.4 Hz),
᎐
᎐
2
2
2
H P
5.12, 5.92, 6.01 (ABC, 3 H, CH᎐CCH CH᎐CH). 19F NMR: δ
᎐
᎐
2
Ϫ121.8 (m, o-F ), Ϫ157.3 (t, p-F, JF F = 20.1 Hz) and Ϫ161.5 (m,
m-F ). FAB mass spectrum: m/z = 1057 (100, Mϩ), 723 (90,
[M Ϫ 2C F ]ϩ) and 658 (98%, [Au{(SPPh ) C᎐CH }]ϩ).
᎐
6
5
2
2
2
[Au(C6F5)2{(SPPh2)2CCH2OEt}] 6. To a dichloromethane
solution (20 cm3) of complex 2 (0.218 g, 0.2 mmol) under nitro-
gen was added a freshly prepared solution of NaOEt (0.2
mmol). After stirring for 3 h the NaClO4 was filtered off and
the solution was concentrated to ca. 5 cm3. Addition of hexane
led to the precipitation of complex 6 as a yellow solid (0.068 g,
33%) (Found: C, 46.8; H, 2.85; S, 6.15. Calc. for C40H27-
AuF10OP2S2: C, 46.35; H, 2.6; S, 6.2%). 31P-{1H} NMR: δ 38.0
18 R. Usón, A. Laguna and M. L. Arrese, Synth. React. Inorg. Metal-
Org. Chem., 1984, 14, 557.
19 G. M. Sheldrick, SHELXL 93, A program for crystal structure
refinement, University of Göttingen, 1993.
1
3
(s). H NMR: δ 0.82 (t, 3 H, OCH2CH3, JH H = 7.0), 2.67 (q, 2
H, OCH2CH3) and 3.47 (t, 2 H, P2CCH2, JH P = 24.7 Hz). 19F
Received 15th May 1997; Paper 7/03357E
3
3518
J. Chem. Soc., Dalton Trans., 1997, Pages 3515–3518