Phosphinethiolate tin(IV)-11 group-metal derivatives. X-ray structure of [Au2Sn(tBu)2(C6F5)2(SC6H4PPh2)2]

Article abstract of DOI:10.1016/S0022-328X(98)00508-7

[SnR₂Cl₂] reacts with (SC₆H₄PPh₂)^- giving [SnR₂(SC₆H₄PPh₂)₂] (R=Me, ^tBu, Ph) (1a-c). These compounds can displace tetrahydrothiophene from [Au(C₆F₅)(tht)] or [Au(tht)₂]ClO₄ or reacts with AgClO₄. Complexes [SnR₂{(SC₆H₄PPh₂)Au(C₆F₅)}₂] (2a-c) and [SnR₂(SC₆H₄PPh₂)₂M]ClO₄ (M=Au 3a-c; M=Ag 4a-c) are obtained. The crystal structure of [Sn(^tBu)₂{(SC₆H₄PPh₂)Au(C₆F₅)}₂] (2b) has been established by X-ray diffraction.

Full text of DOI:10.1016/S0022-328X(98)00508-7

Journal of Organometallic Chemistry 574 (1999) 207–212
Phosphinethiolate tin(IV)-11 group-metal derivatives. X-ray structure
of [Au2Sn(tBu)2(C6F5)2(SC6H4PPh2)2]1
Eduardo J. Ferna´ndez a, Michael B. Hursthouse b, Mariano Laguna c,*, Raquel Terroba a,b
a Departamento de Qu´ımica, Uni6ersidad de la Rioja, 26001 Logron˜o, Spain
b Department of Chemistry, Uni6ersity of Wales Cardiff, PO Box 912, Cardiff CF1 3TB, UK
c Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n, Uni6ersidad de Zaragoza-C.S.I.C., 50009 Zaragoza, Spain
Received 6 August 1997; received in revised form 13 February 1998
Abstract
t
[SnR2Cl2] reacts with (SC6H4PPh2)− giving [SnR2(SC6H4PPh2)2] (R=Me, Bu, Ph) (1a–c). These compounds can displace
tetrahydrothiophene from [Au(C6F5)(tht)] or [Au(tht)2]ClO4 or reacts with AgClO4. Complexes [SnR2{(SC6H4PPh2)Au(C6F5)}2]
(2a–c) and [SnR2(SC6H4PPh2)2M]ClO4 (M=Au 3a–c; M=Ag 4a–c) are obtained. The crystal structure of [Sn(tBu)2{(SC6H4-
PPh2)Au(C6F5)}2] (2b) has been established by X-ray diffraction. © 1999 Elsevier Science S.A. All rights reserved.
Keywords: Tin; Gold; Silver; Phosphinethiolate; Heteronuclear complexes
1. Introduction
phosphines in these complexes enlarge their properties
and phosphine-complex chemistry is the basis for a
variety of catalytic reactions [6]. The development of
these two fields of research led to the recent interest in
mixed-donor phosphorus–sulphur ligands not only for
the possible addition of the above mentioned proper-
ties, but also for the potential preparation of new
heteronuclear complexes due to the different coordina-
tion properties of the P and S ends [7]. These type of
derivatives with transition and main group metal cen-
ters and no metal–metal bond are very important for
their new reactivity patterns [8].
Phosphorus–thioether chelates have been studied by
the research groups of Meek [9], Clark [10], Roundhill
[11], Sanger [12] among others [13] but the chemistry of
phosphinethiol ligands has received less attention. In
this paper we report the preparation of tin complexes
with (SC6H4PPh2)−, and the new compounds
[SnR2(SC6H4PPh2)2] were used for the synthesis of het-
eropolynuclear complexes with 11 group metals. The
structure of [Sn(tBu)2{(SC6H4PPh2)Au(C6F5)}2] has
been established by X-ray diffraction.
Transition metal complexes containing thiolates and
thioethers have received a great deal of attention be-
cause they are involved in both enzymatic [1] and
catalytic [2] processes, besides having some important
applications in medicine, as in the case of gold com-
plexes for the treatment of rheumatoid arthritis [3] with
thiomalategold(I) (Myocrysin) or the triethylphosphine
gold(I) thioglucose derivative Auranofin ([2,3,4,6-tetra-
O-acetyl-1-thio-h-D-glucopyranosal-S) (triethylphos-
phine)gold(I)]. In addition Auranofin has proved to be
an effective cytotoxic agent against melanoma and P388
leukaemia cells [4] and, which is more important, au-
rothioglucosa and aurothiomalate have anti-HIV-1 ac-
tivity in vitro [5]. On the other hand, the presence of
* Corresponding author. Tel.:+34 976 761181; fax: +34 976
761187; e-mail: mlaguna@posta.unizar.es
1 Dedicated to Professor P. Royo on the occasion of his 60th
birthday.
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00508-7

208
E.J. Ferna´ndez et al. / Journal of Organometallic Chemistry 574 (1999) 207–212
Table 1
Data for the new compounds
Complex
Yield (%)
Analyses (%)a
31P{1H}e
C
H
S
LMb
f
M.p. (°C)
138
(J)
1a [SnMe2(SC6H4PPh2)2]
82
63
94
61
59
68
82
76
45
70
61
50
61.7
4.9
(4.65)
5.25
(5.65)
4.15
(4.45)
2.3
(2.35)
2.65
(3.0)
2.3
(2.4)
2.75
(3.3)
3.75
(4.15)
2.95
(3.3)
3.7
(3.65)
4.65
(4.5)
3.4
8.35
(8.7)
7.8
−12.5(s)
(75.7)
−12.5(s)
(62.05)
64.05
(64.5)
66.7
(67.05)
40.75
(41.05)
43.75
(43.45)
45.85
(45.4)
43.8
(44.25)
46.95
(47.35)
49.45
(49.8)
47.75
(48.4)
51.1
1b [SntBu2(SC6H4PPh2)2]
2
172
(7.8)
6.85
(7.45)
4.1
(4.4)
4.45
(4.15)
4.1
(4.05)
5.75
(6.2)
5.85
(5.75)
5.25
(5.55)
6.15
(6.8)
6.45
(6.25)
5.9
1c [SnPh2(SC6H4PPh2)2]
3
147
−13.8(s)
(101.9)
37.0(s)
2a [SnMe2{(SC6H4PPh2)Au(C6F5)}2]
2b [SntBu2{(SC6H4PPh2)Au(C6F5)}2]
2c [SnPh2{(SC6H4PPh2)Au(C6F5)}2]
3a [SnMe2(SC6H4PPh2)2Au]ClO4
3b [SntBu2(SC6H4PPh2)2Au]ClO4
3c [SnPh2(SC6H4PPh2)2Au]ClO4
4a [SnMe2(SC6H4PPh2)2Ag]ClO4
4b [SntBu2(SC6H4PPh2)2Ag]ClO4
4c [SnPh2(SC6H4PPh2)2Ag]ClO4
3
117
6
112
35.6(s)
36.2(s)
35.4(s)
35.9(s)
36.9(s)
15
88
99
85
36c
33c
41c
99
133d
162d
158d
154d
116d
158d
4.6(dd)
(443.3) (511.6)
5.7(dd)
(441.8) (508.3)
5.2(dd)
(51.45)
53.65
(54.05)
(3.6)
(6.0)
(471.1) (543.7)
a Calculated values are given in parentheses.
b In acetone, values in V−1cm2 mol−1
c In dichloromethane.
.
d Decompose without melting.
e In CDCl3 l in ppm., J in Hz.
2. Results and discussion
[M-SC6H4PPh2]+ and [M-2R-SC6H4PPh2]+ are present
in accordance with the formulation.
Recently [14] we have described the preparation of
dithiolate tin complexes by metathetical reaction of
[SnR2Cl2] with the dithiolate disodium salt. Likewise
the reaction of [SnR2Cl2] with NaSC6H4PPh2 in a 1:2
ratio, affords compounds 1a–c in good yields (Eq. (1)).
With these data we propose a tetracoordinated
SnC2S2 core for the tin compounds, the phosphorus
atoms being uncoordinated. The presence of these free
donor-atoms gives the possibility of using the com-
plexes 1a–c as starting materials in the synthesis of
heterometallic derivatives. The reaction of the tin com-
pounds 1a–c with [Au(C6F5)(tht)] in a 1:2 ratio gives
trinuclear complexes (Eq. (2)).
[SnCl2R2]+2HSC6H4PPh2
EtOH
“ 2HCl+[SnR2(SC6H4PPh2)2]
NaOEt
t
R=Me 1a, Bu 1b, Ph 1c
(1)
[SnR2(SC6H4PPh2)2]+2[Au(C6F5)(tht)]
The 1H-NMR spectra of compounds 1a–b show
singlets due to the methyl and tert-butyl radicals
bonded to the metal showing tin satellites. In the
31P{1H}-NMR a singlet in negative values of l is
observed in all the cases, with a similar l to the starting
phosphine (l= −13.1 ppm) [15] (Table 1). In the
methyl and phenyl derivatives, these singlets appear
with the satellites from the tin active nuclei (117Sn and
119Sn), but the constant values 75.7 and 42.3 Hz are not
in accordance with a Sn–P bond (ca. 1350 Hz [16]), and
“[SnR2{(SC6H4PPh2)Au(C6F5)}2]+2tht
t
R=Me (2a), Bu (2b), Ph (2c)
(2)
After coordination, the 31P{1H}-NMR spectra show
a broad singlet (probably because the coupling with the
fluorine atoms) for all these new compounds with l
values typical of Au–P complexes (Table 1, Dl:50
1
ppm) and the H-NMR spectra show singlets for the
methyl groups of complexes 2a–b higher field displaced
from the mononuclear tin derivatives. Whereas the
proton-NMR spectra show tin satellites, they are ab-
sent in the phosphorus NMR. The three resonances in
4
must be a JSn–P. The mass spectra (LSIMS+) of these
compounds show no peaks of their parent ion but

E.J. Ferna´ndez et al. / Journal of Organometallic Chemistry 574 (1999) 207–212
209
Fig. 1. Molecule of compound 2b in the crystal. Displacement parameter ellipsoids represent 50% probability surfaces. H atoms are omitted for
clarity.
19F-NMR spectra in 2:1:2 ratio are in agreement with
equivalent pentafluorophenyl groups bonded to a gold(I)
center. Although complexes 2a–c behave as non con-
ducting in acetone solution their LSIMS mass spectra do
not show peaks corresponding to heteronuclear species
except for 2b which show peaks at m/z 1380 (6%)
[M-C6F5]+ and 1038 (7%) [M-SC6H4PPh2–C6F5]+.
The molecular structure of the complex [Au2Sn
(C6F5)t2Bu2(SC6H4PPh2)2] 2b, has been established by
X-ray diffraction and is shown in Fig. 1. Atomic coordi-
nates are given in Table 2 and selected bond lengths and
angles in Table 3. Every phosphinethiolate ligand is
bridging the tin center and one of the gold atoms. The
tin(IV) is bonded to the sulphur atoms of the P,S-donor
ligands with distances Sn–S(1)=2.444(3) and Sn–
˚
and Au(2)–C(7)=2.013(11) A, and are in the range of
˚
the latter compounds 2.057 and 2.053 A. The tin–gold
distances are Sn–Au(1)=5.08 and Sn–Au(2)=5.48 A,
˚
so there are no significant interactions between the
metallic centers.
The formation of heteronuclear tin complexes can be
extended reacting complexes 1a–c with [Au(tht)2]ClO4
and AgClO4 in a 1:1 molar ratio (Eqs. (3) and (4)).
[SnR2(SC6H4PPh2)2]+[Au(tht)2]ClO4
“[SnR2(SC6H4PPh2)2Au]ClO4+2tht
t
R=Me (3a), Bu (3b), Ph (3c)
[SnR2(SC6H4PPh2)2]+AgClO4
(3)
“[SnR2(SC6H4PPh2)2Ag]ClO4
t
˚
S(2)=2.434(3) A and to the tert-butyl groups with bond
R=Me (4a), Bu (4b), Ph (4c)
(4)
lengths Sn–C(20)=2.194(11) and Sn–C(30)=2.197(12)
A similar to other Sn(IV)–C compounds [17] and is in
The acetone solutions of the gold complexes 3a–c
show conductivity values in agreement with a formula-
tion as 1:1 electrolytes [19]; Complexes 4a–c are not
enough soluble in acetone and their conductivities has
been measured in dichloromethane solutions, showing
values characteristic of 1:1 electrolytes (Table 1) [20]. The
IR spectra of these new derivatives show bands at 1100
(vs, br) and 620 (m) cm−1 indicating ionic ClO4 [21]. The
1H-NMR of complexes 3 and 4 show singlets for the
methyl groups at lower field than in the starting materi-
als. The 31P{1H}-NMR show a sharp singlet for the
complexes 3a–c and a doublet of doublets for 4a–c
because of the two active silver nuclei (Table 1). The
coupling constants are in the range of 508.3–543.7 Hz
˚
a distorted tetrahedral arrangement with angles C(20)–
Sn–C(30)=122.3(5), C(20)–Sn–S(2)=98.1(3), C(30)–
Sn–S(2)=110.7(3), C(20)–Sn–S(1)=112.3(3), C(30)–
Sn–S(1)=101.0(3) and S(2)–Sn–S(1)=113.01(11)°.
The ‘SntBu2(SC6H4PPh2)2’ unit acts as a bridging ligand
between two ‘Au(C6F5)’ fragments. The gold(I) atoms
are in
a linear coordination, C(1)–Au(1)–P(1)=
177.5(3)° and C(7)–Au(2)–P(2)=176.0(3)°. The gold–
phosphorus bond lengths are Au(1)–P(1)=2.269(3) and
˚
Au(2)–P(2)=2.270(3) A and are similar to those found
˚
in [Au(C6F5)(PPh2CH(PPh2Me)] 2.287(2)
A
and
˚
[Au(C6F5){PPh2CH(PPh2Me)Au(C6F5)}] 2.286(4)A [18].
1
1
The gold–carbon distances are Au(1)–C(1)=2.052(10)
for J109Ag–P and 441.8–471.1 Hz for J107Ag–P which

210
E.J. Ferna´ndez et al. / Journal of Organometallic Chemistry 574 (1999) 207–212
Table 2
Table 2 (Continued)
Atomic coordinates (×10−4) and equivalent isotropic displacement
2
3
˚
parameters (A ×10 ) for 2b
x
y
z
Ueq
x
y
z
Ueq
C(233)
C(234)
C(235)
C(236)
C(20)
C(21)
C(22)
C(23)
C(30)
C(31)
C(32)
C(33)
6033(9)
5358(9)
5131(9)
5616(9)
4164(12)
4172(14)
5267(15)
3372(14)
2365(10)
2490(13)
2358(16)
1355(14)
3394(10)
3325(10)
4010(10)
4770(9)
6510(11)
7654(12)
5726(15)
6521(15)
6896(10)
6297(14)
8005(13)
7072(17)
514(7)
1096(6)
1544(6)
1447(6)
3578(6)
3190(8)
3948(9)
4161(9)
1930(6)
1338(8)
1557(10)
2332(10)
37(3)
36(3)
34(3)
27(2)
41(3)
66(5)
82(6)
78(5)
36(3)
74(5)
90(6)
93(6)
Sn(1)
Au(1)
Au(2)
S(1)
S(2)
P(1)
P(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
F(2)
F(3)
F(4)
F(5)
F(6)
3784(1)
1978(1)
5592(1)
3523(2)
5428(3)
3149(2)
6900(2)
961(8)
5898(1)
4471(1)
7597(1)
4174(2)
5618(3)
2703(2)
5842(2)
6095(9)
6695(9)
7798(11)
8400(10)
7823(10)
6727(9)
6175(6)
8356(7)
9496(6)
8422(6)
6211(6)
9110(9)
9691(10)
10637(10)
11090(10)
10577(10)
9642(9)
9258(6)
11149(7)
12056(7)
11045(6)
9166(6)
1750(9)
2145(10)
1423(11)
336(10)
−811(0)
624(9)
2091(9)
2361(11)
1829(15)
1115(11)
868(10)
1329(9)
2549(9)
1751(9)
1634(9)
2278(10)
3104(10)
3242(9)
5609(9)
6383(10)
6213(11)
5327(11)
4534(12)
4668(10)
5451(19)
4382(10)
4176(11)
4953(10)
5998(12)
6297(10)
4831(9)
4120(9)
2713(1)
4759(1)
484(1)
3245(2)
2046(2)
4807(2)
695(2)
4684(6)
5106(6)
5003(7)
4457(8)
4015(7)
4150(6)
5646(3)
5434(5)
4355(6)
3439(4)
3704(4)
353(6)
27(1)
27(1)
26(1)
31(1)
37(1)
23(1)
24(1)
25(2)
30(3)
42(3)
48(3)
40(3)
26(3)
40(2)
66(2)
78(3)
59(2)
43(2)
26(2)
38(3)
47(4)
52(4)
40(3)
26(3)
59(2)
84(3)
90(3)
65(2)
57(2)
27(3)
31(3)
42(3)
37(3)
38(3)
31(3)
23(2)
45(3)
68(5)
49(4)
39(3)
34(3)
27(3)
28(3)
32(3)
39(3)
33(3)
28(3)
28(3)
34(3)
47(3)
44(3)
47(3)
34(3)
26(2)
38(3)
45(3)
37(3)
44(3)
34(3)
26(2)
31(3)
1135(9)
572(10)
−232(11)
−442(9)
132(9)
1968(5)
784(6)
−825(7)
−1195(6)
−96(5)
4377(9)
3660(11)
2802(11)
2544(11)
3192(11)
4032(9)
3885(7)
2159(8)
1643(7)
2877(7)
4661(7)
3333(9)
3306(9)
3506(10)
3697(9)
3705(9)
3529(9)
2770(8)
1707(9)
1435(11)
2177(11)
3245(10)
3541(9)
4515(9)
5405(9)
6412(9)
6564(9)
5683(9)
4672(9)
7784(9)
7486(10)
8152(12)
9106(11)
9407(10)
8765(9)
7747(8)
8177(10)
8748(11)
8951(10)
8580(10)
7937(10)
6315(9)
6525(9)
are very close to those reported for a P2S2 tetracoordi-
nation of silver complexes [22].
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
F(8)
The mass spectra of complexes 3a–c and 4a–b show
in all complexes the peak corresponding with the
cation formulation [M-ClO4]+, furthermore others
corresponding with the lack of one or two organic
groups bonded to tin are also present.
Based on all these data and the well known prefer-
ence of silver(I) for tetracoordination, a structure with
the silver atom with P,P,S,S-coordination likewise to
the reported TiCp2(S–P)2 unit [7] could be possible for
complexes 4a–c. Because of the preferred two-coordi-
nation of gold(I), it could be proposed for complexes
3a–c, a polymer chain or an heterodinuclear structure,
with the gold centers in a linear arrangement.
−300(6)
−367(8)
215(9)
864(7)
907(6)
−894(4)
F(9)
−1015(5)
143(6)
F(10)
F(11)
F(12)
C(111)
C(112)
C(113)
C(114)
C(115)
C(116)
C(121)
C(122)
C(123)
C(124)
C(125)
C(126)
C(131)
C(132)
C(133)
C(134)
C(135)
C(136)
C(211)
C(212)
C(213)
C(214)
C(215)
C(216)
C(221)
C(222)
C(223)
C(224)
C(225)
C(226)
C(231)
C(232)
1452(4)
1552(4)
5733(6)
6352(6)
7076(7)
7201(6)
6598(7)
5862(6)
4186(5)
4057(7)
3610(9)
3276(7)
3387(6)
3857(6)
4550(6)
5003(6)
4800(6)
4152(7)
3679(6)
3866(6)
−69(6)
−765(6)
−1350(7)
−1257(7)
−570(7)
31(6)
3. Experimental section
The C, H, S analyses were carried out on a Perkin–
Elmer 2400 Microanalyser. Conductivities were mea-
sured in approximately 5×10−4 mol dm−3 acetone
solutions, with a Jenway 4010 Conductimeter. The
melting points were measured in a Gallekamp appara-
tus and are uncorrected. The infrared spectra were
recorded (4000–200 cm−1) on Perkin–Elmer 883
Spectrophotometer, using Nujol mulls between
polyethylene sheets. The NMR spectra were recorded
on Bruker ARX 300 Spectrometer, in CDCl3. Chemi-
cal shifts are cited relative to SiMe4 (1H), 85% H3PO4
(external 31P) and CFCl3 (19F). Mass spectra were
recorded on VG Autospec with LSIMS (Liquid Sec-
ondary Ion Mass Spectrometry) technique using 3-ni-
trobenzylalcohol as matrix and a caesium gun. The
elemental analyses, conductivities, yield, melting point
and 31P{1H} data of the new complexes are listed in
Table 1.
1511(6)
1998(6)
2646(7)
2823(7)
2363(7)
1702(6)
870(6)
417(6)

E.J. Ferna´ndez et al. / Journal of Organometallic Chemistry 574 (1999) 207–212
211
Table 3
Selected bond lengths (A) and angles (°) for 2b
NMR: l=7.91, 7.17 and 6.73 (m, 8H, C6H4),
˚
2
7.59–7.31 (m, 20H, Ph), 0.27 (s, JSn–H=61.2Hz, 6H,
Me); 19F-NMR: l= −115.5 (m, 4F, Fo), −158.4 (t,
3JFpFm=19.6 Hz, 2F, Fp), −162.3 (m, 4F, Fm). 2b
l=8.18, 7.12 and 6.79 (m, 8H, C6H4), 7.66−7.28 (m
Sn(1)–C(20)
2.194(11) Sn(1)–C(30)
2.197(12)
Sn(1)–S(2)
Au(1)–C(1)
2.434(3) Sn(1)–S(1)
2.052(10) Au(1)–P(1)
2.4443)
2.2693)
t
20H, Ph), 0.95 (s, 3JSn–H=36.2 Hz, 18H, Bu); 19F-
3
NMR: l= −115.3 (m, 4F, Fo), −159.0 (t, JFpFm
=
Au(2)–C(7)
S(1)–C(136)
2.013(11) Au(2)–P(2)
1.787(12) S(2)–C(236)
2.2703)
20.0 Hz, 2F, Fp), −162.8 (m, 4F, Fm). 2c
l=7.78–7.03 and 6.59 (m, 38H, C6H4); 19F-NMR:
1.765(10)
3
l= −115.0 (m, 4F, Fo), −159.4 (t, JFpFm=20.2 Hz,
2F, Fp), −162.6 (m, 4F, Fm).
C(20)–Sn(1)–C(30) 122.3(5)
C(20)–Sn(1)–S(2)
C(20)–Sn(1)–S(1)
S(2)–Sn(1)–S(1)
C(7)–Au(2)–P(2)
C(236)–S(2)–Sn(1) 112.5(4)
C(121)–P(1)–Au(1) 114.5(4)
C(221)–P(2)–Au(2) 112.2(3)
C(211)–P(2)–Au(2) 115.0(4)
C(2)–C(1)–Au(1)
C(8)–C(7)–Au(2)
C(22)–C(20)–Sn(1) 110.1(9)
C(32)–C(30)–Sn(1) 109.5(9)
C(31)–C(30)–Sn(1) 106.5(9)
98.1(3)
112.3(3)
113.0(1)
179.0(3)
C(30)–Sn(1)–S(2)
C(30)–Sn(1)–S(1)
C(1)–Au(1)–P(1)
110.7(3)
101.0(3)
177.5(3)
3.1.3. [MSnR2(SC6H4PPh2)2]ClO4 [M=Au R=Me
t
t
(3a), Bu (3b), Ph (3c), M=Ag R=Me (4a), Bu (4b),
Ph (4c)]
C(136)–S(1)–Sn(1) 106.0(4)
C(111)–P(1)–Au(1) 112.6(4)
C(131)–P(1)–Au(1) 114.9(3)
C(231)–P(2)–Au(2) 110.4(4)
To a dichloromethane (M=Au) or acetone (M=
Ag) solution (20 cm3) of 1a (0.074 g, 0.1 mmol), 1b
(0.082 g, 0.1 mmol) or 1c (0.086 g 0.1 mmol) was added
[Au(tht)2]ClO4 (0.047 g, 0.1 mmol) or AgClO4 (0.021 g,
0.1 mmol). After 2 h stirring the solutions were concen-
trated in vacuum and the addition of hexane affords the
precipitation of the new compounds as white solids.
1H-NMR: 3a l=7.88–7.04 and 6.85 (m, 28H, Ph),
0.91 (s, 2JSn–H=62.2Hz, 6H, Me). 3b l=7.76, 7.26 and
6.94 (m, 8H, C6H4), 7.61–7.42 (m, 20H, Ph), 1.30 (s,
C(6)–C(1)–Au(1)
123.3(7)
122.6(8)
123.2(8)
C(12)–C(7)–Au(2) 125.2(8)
C(23)–C(20)–Sn(1) 108.4(9)
C(21)–C(20)–Sn(1) 107.5(8)
C(33)–C(30)–Sn(1) 111.1(9)
t
3JSn–H=40.2Hz, 18H, Bu). 3c l=7.65–7.05 and 6.78
3.1. Syntheses
1
(m, 28H, Ph). 4a H-NMR: l=7.76 and 7.63–7.09 (m,
The starting materials (HSC6H4PPh2) [15],
[Au(C6F5)(tht)] [23] (tht=tetrahydrothiophen), and
[Au(tht)2]ClO4 [24] were prepared as described previ-
ously. All other reagents were commercially available.
28H), 0.82 (s, 6H, Me). 4b l=7.83 and 6.96 (m, 8H,
C6H4), 7.52–7.30 (m, 20H, Ph), 1.24 (s, 18H, Bu). 4c
t
l=7.65–7.05, 6.94 and 6.78 (m, 28H, Ph). Mass spec-
tra m/z (%) [M-ClO4]+, [M-ClO4-R]+ and [M-ClO4-
2R]+ 3a 933 (100), no peak and 903 (11); 3b 1017 (41),
no peak and 903 (23); 3c 1057 (80), 980 (42) and 903
(45); 4a 841 (11), 826 (4) and 811 (4); 4b 927 (53), 870
(30) and 811 (32).
t
3.1.1. [SnR2(SC6H4PPh2)2] [R=Me (1a), Bu (1b), Ph
(1c)]
To a solution of (HSC6H4PPh2) (0.294 g, 1 mmol) in
EtOH and EtONa (20 cm3, 0.1M) is added [SnCl2R2]
t
[R=Me (0.110 g, 0.5 mmol), Bu (0.152 g, 0.5 mmol),
Ph (0.172 g, 0.5 mmol)]. After stirring 5 h the new
compounds are filtered as white solids. H-NMR: 1a
3.2. Crystal structure determination of compound 2b
1
Single crystals were grown by diffusing hexane into a
dichloromethane solution of complex [Au2Sn(C6F5)2-
tBu2(SC6H4PPh2)2] 2b at r.t., and mounted in inert oil.
l=7.57, 7.06 and 6.69 (m, 8H, C6H4), 7.33–7.16 (m,
2
20H, Ph), 0.66 (s, JSn–H=62.2Hz, 6H, Me). 1b l=
7.74, 7.05 and 6.70 (m, 8H, C6H4), 7.30–7.11 (m, 20H,
3
t
Ph), 1.20 (s, JSn–H=42.3Hz, 18H, Bu). 1c l=7.66,
6.99 and 6.49 (m, 8H, C6H4) 7.44–7.11 (m, 30H, Ph).
Mass spectra m/z (%) [M-SC6H4PPh2]+ and [M-2R-
SC6H4PPh2]+: 1a 441 (100) and 411 (15). 1b 527 (60)
and 411 (100). 1c 565 (41) and 411 (15).
3.2.1. Crystal data and data collection parameters
2b C56H46Au2F10P2S2Sn, M=1547.61, triclinic, a=
13.654(5), b=13.679(7), c=18.645(7) A, h=73.37(3),
˚
3
˚
i=86.12(3), k=65.86(3)°, U=3040(2) A , T=150 K,
space group P1, graphite monochromated Mo–Kh ra-
diation u=0.71069 A, Z=2, Dcalc=1.691 mg m−3
,
˚
3.1.2. [Au2Sn(C6F5)2R2(SC6H4PPh2)2] [R=Me (2a),
tBu (2b), Ph (2c)]
F(000)=1484, colourless prism with dimensions
0.24×0.22×0.18 mm, v=5.407 mm−1; Delft Instru-
ments FAST TV area detector diffractometer posi-
tioned at the window of a rotating-anode generator,
following procedures described elsewhere [25], q range
for data collection 1.76 to 25.12°, −165h516,
−155k516, −215l514; 12849 reflections col-
lected, 8332 independent (Rint=0.063).
To a dichloromethane solution (20 cm3) of 1a (0.074
g, 0.1 mmol), 1b (0.082 g, 0.1 mmol) or 1c (0.086 g, 0.1
mmol) was added [Au(C6F5)(tht)] (0.090 g, 0.2 mmol).
After 2 h stirring the solutions were concentrated in
vacuum and the addition of hexane affords the precipi-
1
tation of the new compounds as white solids. 2a H-

212
E.J. Ferna´ndez et al. / Journal of Organometallic Chemistry 574 (1999) 207–212
[5] (a) T. Okada, B.K. Patterdon, O.S. Ye, M.E. Gurney, Virology
192 (1993) 631. (b) H.A. Blough, M. Richetti, B.H. Montagnier,
Chem. Abstr. 115 (1991) 174630p.
3.2.2. Structure solution and refinement
The structure was determined using the PATT in-
struction of SHELXS 86 [26], the structure were refined
by full-matrix least squares on F2o, using the program
SHELXL93 [27]. All data used were corrected for
Lorentz-polarization factors, and subsequently for ab-
sorption using the program DIFABS [28]. The non-hy-
drogen atoms were refined with anisotropic thermal
parameters. All hydrogen atoms were included in ide-
alised positions. Refinement proceeded to R=0.0499,
wR=0.1475 and goodness of fit on F2 1.080 for 664
parameters and 12 restraints, and R=0.0565, wR=
0.1494 for all data. In the final Fourier synthesis the
[6] (a) L.H. Pignolet (Ed.), Homogeneous Catalysis with Metal
Phosphine Complexes, Plenum Press, New York, 1983. (b) M.C.
Simpson, D.J. Colehamilton, Coord. Chem. Rev. 155 (1955) 163.
[7] (a) G.S. White, D.W. Stephan, Organometallics 6 (1987) 2169.
(b) G.S. White, D.W. Stephan, Inorg. Chem. 24 (1985) 1499. (c)
G.S. White, D.W. Stephan, Organometallics 7 (1988) 903.
[8] D.E. Stephan, Coord. Chem. Rev. 95 (1989) 41.
[9] (a) P.G. Eller, J.M. Ricker, D.W. Meek, J. Am. Chem. Soc. 95
(1973) 3540. (b) D.W. Meek, Inorg. Nucl. Chem. Lett. 5 (1969)
235.
[10] J.D. Orbell, G.R. Clark, J. Organomet. Chem. 215 (1981) 121.
[11] D.M. Roundhill, S.G.N. Roundhill, W.B. Breaulieu, U. Bagchi,
Inorg. Chem. 19 (1980) 3365.
electron density fluctuates in the range 3.342 to −1.350
[12] A. Sanger, Can. J. Chem. (1983) 2214.
−3
˚
e A
.
[13] (a) N. Froelich, P.B. Hitchcock, J. Hu, M.F. Lappert, J. R.
Dilworth, J. Chem. Soc. Daton Trans. (1966) 1941. (b) F.
Morandini, P. Rigo, M. Bressau, J. Organomet. Chem. 247
(1983) C8. (c) M. Bressan, G. Polzonetti, C. Furlani, Polyhedron
2 (1983) 523. (d) T. Gerdan, R. Kramolowsky, Z. Naturforsch B,
Anorg. Chem. Org. Chem. (1982) 332. (e) T.N. Lockyer, Aust. J.
Chem. 27 (1974) 259.
Tables of thermal parameters and observed and cal-
culated structure factors have been deposited at the
Cambridge Crystallographic Data Centre.
[14] E. Cerrada, E.J. Ferna´ndez, M.C. Gimeno, A. Laguna, M.
Laguna, M.D. Villacampa, J. Organomet. Chem. 492 (1995) 105.
[15] E. Block, G. Ofori-Okai, J. Zubieta, J. Am. Chem. Soc. 111
(1989) 2327.
[16] J. Mason, Multinuclear NMR, Plenum Press, New York and
London, 1987, pp 318–22.
[17] (a) A.G. Davies, in: G. Wilkinson, F.G.A. Stone, E.W. Abel
(Eds.), Comprehensive Organometallic Chemistry II, vol 2, Perg-
amon, Oxford, 1995. (b) R. Rulkens, A.J. Lough, I. Manners,
Angew. Chem. Int. Ed. Engl. 35 (1996) 1805. (c) R.J. Batchelor,
F.W.B. Einstein, C.H.W. Jones, R.D. Sharma, Inorg. Chem. 27
(1988) 4636. (d) M. Weidenbruch, J. Schlaetke, K. Peters, H.G.
von Schnering, J. Organomet. Chem. 414 (1991) 319.
[18] R. Uso´n, A. Laguna, M. Laguna, I. La´zaro, A. Morata, P.G.
Jones, G.M. Sheldrick, J. Chem. Soc. Dalton Trans. (1986) 669.
[19] W.J. Geary, Coord. Chem. Rev. 7 (1971) 81.
Acknowledgements
The Spanish authors thank the Direccio´n General de
Investigacio´n Cient´ıfica y Te´cnica (PB95- 0140) for
financial support and Ministerio de Educacio´n y Cul-
tura for a grant (to R.T.), and M.B.H. thanks the
Engineering and Physical Sciences Research Council for
support of the X-ray facilities.
References
[1] H. Holm, J.A. Ibers, Science 209 (1980) 223.
[2] (a) Ph. Kalck, Organometallic in Organic Synthesis in: A. de
Meijere, H.T. Dieck (Ed.), Springer Verlag, Heidelberg, 1987, p.
297. (b) S Cladiali, J.C. Bayo´n, C. Claver, Tetrahedron Asymm.
6 (1995) 1453. (c) J.R. Dilworth, Coord. Chem. Rev. 154 (1996)
163
[20] M. Contel, PhD Pamplona, 1996.
[21] M.N. Gowda, S.B. Naikan, G.K.N. Reddy, Adv. Inorg. Chem.
Radiochem. 28 (1984) 255.
[22] A.R.J. Gence, A.M. Gibson, N.K. Guymer, G. Reid, J. Chem.
Soc. Dalton Trans. (1996) 4099.
[3] (a) K. Lande´, Mu¨nchener Med. Wochenschr. 74 (1927) 1132. (b)
J. Forestier, Bull. Me´m. Soc. Me´d. Hop (Par´ıs) 53 (1929) 323. (c)
D.R. Haynes, M.N. Whitehouse, in: K.D. Rainsforth, G.P. Velo
(Eds.), Anti-Rheumatic Therapy, Kluwer, Dordrecht, 1989, p.
207. (d) C.F. Shaw III, A.A. Isab, J.D. Hoeschele, M. Starich, J.
Jocke, P. Schulteis, J. Xiao, J. Am. Chem. Soc. 116 (1994) 2254.
(e) G.C. Graham, G.D. Champion, J.B. Ziegher, Inflammor-
pharmacology 1 (1991) 99.
[23] R. Uso´n, A. Laguna, J. Vicente, J. Chem. Soc. Chem. Commun.
(1976) 353.
[24] R. Uso´n, A. Laguna, M. Laguna, J. Jime´nez, M.P. Go´mez, A.
Sainz, P.G. Jones, J. Chem. Soc. Dalton Trans. (1990) 3457.
[25] A.A. Danopoulos, G. Wilkinson, B. Hussain-Bates, M.B. Hurst-
house, J. Chem. Soc. Dalton Trans. (1991) 1855.
[26] G.M. Sheldrick, SHELXS 86, Acta Crystallogr. Sect. A, 46
(1990) 467.
[4] (a) O.M.N. Dhubhghaill, P.J. Sadler, Metal complexes, in: B.K.
Keppler (Ed.), Cancer Chemotherapy, VCH, Weinhein, 1993. (b)
C.K. Mirabelli, R.K. Johnson, D.T. Hill, L.F. Faucette, G.R.
Girard, G.Y. Kuo, C.M. Sung, S.T. Crooke, J. Med. Chem. 29
(1986) 218.
[27] G.M. Sheldrick, SHELXL 93, Programm for Crystal Structure
Refinement. University of Go¨tingen, Germany, 1993.
[28] N.P.C. Walker, D. Stuart, Acta Crystallogr. Sect. A. 39 (1983)
158. (adapted for FAST geometry by A. Karaulov, University of
Wales, Cardiff, 1991).
.