Synthesis of heteropolynuclear complexes using new tin(IV) dimers. X-ray structure of [AuSnCl(tBu)2(SC6H4)(PPh 3)]

Article abstract of DOI:10.1021/om970326p

Li₂(SC₆H₄) reacts with [SnR₂Cl₂] affording the dinuclear derivatives [{SnR₂(SC₆H₄)}₂] (R = Me, ^tBu, Ph) (1a-c). The reaction of these dimer derivatives with various [AuClL] breaks the tin-sulfur bonds, affording the heterobimetallic complexes [AuSnClR₂(SC₆H₄)L] (L = PPh₃, AsPh₃, CH₂PPh₃) (2-4). The synthesis of [Au{SnClMe₂(SC₆H₄)}₂] (5) is carried out in a similar way. The lithiated product Li₂(SC₆H₄) can react with [AuCl(PPh₃)], giving [Au₂(SC₆H₄)(PPh₃)₂] (6). The molecular structure of the complex [AuSnCl(^tBu)₂(SC₆H₄)(PPh ₃)] (2b) has been established by X-ray diffraction and shows a tetrahedral tin center and a linear gold(I) atom bridged by the "C-S" bidentate ligand.

Full text of DOI:10.1021/om970326p

Organometallics 1997, 16, 5637-5640
5637
Syn th esis of Heter op olyn u clea r Com p lexes Usin g New
Tin (IV) Dim er s. X-r a y Str u ctu r e of
[Au Sn Cl(tBu )2(SC6H4)(P P h 3)]
Eduardo J . Ferna´ndez,† Michael B. Hursthouse,‡ Mariano Laguna,*,§ and
Raquel Terroba†,‡
Departamento de Quı´mica, Universidad de la Rioja, 26001 Logron˜o, Spain, Department of
Chemistry, University of Wales Cardiff, P.O. Box 912, Cardiff CF1 3TB, U.K., and
Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
Received April 16, 1997X
Li2(SC6H4) reacts with [SnR2Cl2] affording the dinuclear derivatives [{SnR2(SC6H4)}2]
t
(R ) Me, Bu, Ph) (1a -c). The reaction of these dimer derivatives with various [AuClL]
breaks the tin-sulfur bonds, affording the heterobimetallic complexes [AuSnClR2(SC6H4)L]
(L ) PPh3, AsPh3, CH2PPh3) (2-4). The synthesis of [Au{SnClMe2(SC6H4)}2] (5) is carried
out in a similar way. The lithiated product Li2(SC6H4) can react with [AuCl(PPh3)], giving
[Au2(SC6H4)(PPh3)2] (6). The molecular structure of the complex [AuSnCl(tBu)2(SC6H4)(PPh3)]
(2b) has been established by X-ray diffraction and shows a tetrahedral tin center and a
linear gold(I) atom bridged by the “C-S” bidentate ligand.
In tr od u ction
pharmaceuticals.7 There are relevant examples of the
latter in gold thiolate chemistry because of antiarthritic
and anticancer activity.8
The synthesis of heteronuclear complexes has at-
tracted much attention in the last two decades, with the
expectation that new reactivity patterns might emerge
from the combination of disparate metals in a single
species.1 The early-late complexes are the most stud-
ied, with examples of transition/main group metal
derivatives being less abundant.2 On the other hand,
thiolate metal complexes are particularly interesting,
not only because they are an important class of hetero-
nuclear complexes but also due to their participation
in central components of the active sites of enzymes such
as ferredoxin and nitrogenase,3 their relevance to metal-
catalyzed hydrodesulfurization,4 and their applications
as fungicides,5 electrical conductors,6 and inorganic
The transmetalation reaction of dithiolate groups
from tin to gold has been successfully carried out in very
mild conditions by our group;9 in contrast, the C-Sn
bond usually is not easily broken, and the transfer of
organic groups to gold requires some palladium catalyst
(Stille reaction).10 The differences in reactivity condi-
tions to transfer S or C ligand ends from tin to other
metals should be a clean way for the preparation of
heteronuclear complexes. If the ligand contains the two
ends, S and C, simultaneously, the partial transfer of
the ligand should afford complexes with the ligand
bridging two metal centers.
We have selected a heterodifunctional S,C-donor
ligand (SC6H42-) bonded to a tin center as a reagent in
a synthetic strategy to form heterodinuclear Sn-Au
derivatives by partial transfer of the thiolate end ligand
to the gold center, whereas the ortho-carbon remains
bonded to the tin atom. In this paper, we report the
synthesis of the tin(IV) dimer compounds [{SnR2-
(SC6H4)}2] (R ) Me, tBu, Ph). From the former, several
heteropolynuclear Au(I)-Sn(IV) complexes have been
obtained, and in the case of [AuSnCl(tBu)2(SC6H4)(PPh3)],
characterization by X-ray diffraction shows a hetero-
metallic ortho-metalated species.
† Universidad de la Rioja.
‡ University of Wales Cardiff.
§ Iniversidad de Zaragoza-C.S.I.C.
X Abstract published in Advance ACS Abstracts, November 15, 1997.
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S0276-7333(97)00326-9 CCC: $14.00 © 1997 American Chemical Society

5638 Organometallics, Vol. 16, No. 26, 1997
Ferna´ndez et al.
Sch em e 1a
F igu r e 1. Molecule of 2a in the crystal. Displacement
parameter ellipsoids represent 50% probability surfaces.
H atoms are omitted for clarity.
the dimer the eight-membered ring which is formed
makes two different groups, endo and exo, inequivalent
(Scheme 1).
a
Key: (i) [SnR2Cl2]. (ii) 2[AuClL]. (iii) PPN[AuCl2]. (iv) ∆,
[AuCl(PPh3)]. (v) 2[AuCl(PPh3)].
The reaction of halogold(I) complexes [AuClL] (L )
PPh3, AsPh3, CH2PPh3) with the tin compounds 1a -c
transfers only the thiolate unit to gold, thus breaking
the dimer. Heterodinuclear derivatives are obtained:
[AuSnClR2(SC6H4)L] (R ) Me, L ) PPh3 (2a ), AsPh3
(3a ), CH2PPh3 (4a ); R ) tBu, L ) PPh3 (2b), AsPh3 (3b),
CH2PPh3 (4b); R ) Ph, L ) PPh3 (2c), AsPh3 (3c),
CH2PPh3 (4c)) (eq ii, Scheme 1). The IR spectra of these
gold-tin complexes show the lack of the characteristic12
ν(Au-Cl) ≈ 350 cm-1 band, suggesting that the thiolate
group has been transferred. The mass spectra (LSIMS+)
do not show peaks corresponding to the molecular ion,
but [M - Cl]+ and [M - R]+ are present, the former
being more abundant than the latter. The 1H NMR
spectra of the methyl complexes show only one signal
corresponding to this group, so now the organic residues
bonded to the tin center are equivalent. The 31P{1H}
NMR show singlets at 37.9, 37.8, and 37.4 ppm for
2a -c, respectively. These data are in accordance with
the existence of a S atom trans to the phosphorus in a
linear coordination of gold(I) (e.g., at 35.6 ppm in
[Au2(S2C6H4)(PPh3)2],13 36.3 ppm in [Au2(S2C6H3C-
H3)(PPh3)2],13 and 36.5 ppm in [Au2(C3S5)(PPh3)2]14). in
contrast with a coordination of the bridging SC6H4 group
through the carbon to the gold center (e.g., 44.9 ppm in
[Au(mes)PPh3]15 and 42.7 ppm in [Au(C6F5)PPh3]).
Complexes 4a -c show singlets at around 30.5 ppm.
The molecular structure of 2a was determined by an
X-ray study and is shown in Figure 1. Selected bond
lengths and angles are given in Table 2. The (SC6H4)2-
ligand is bridging both metals centers, with the S atom
bonded to the gold and the carbon to the tin center. The
gold atom is in a linear coordination typical for gold(I)
complexes, with S-Au-P ) 176.56(11)°. Unlike other
(phosphine)gold(I) thiolate complexes, there are no
intermolecular short gold-gold contacts in the lattice,
probably because the bulkiness of this thiolate-tin
ligand prevents further contacts between gold atoms.
Ta ble 1. Ma ss Sp ectr a l Da ta a for Com p lexes 1a -c
complex
[M]+
[M - R]+ [M - 2R]+ [M - 3R]+ [M - 4R]+
1a dimer
515 (21) 499 (67)
469 (14)
monomer 259 (52) 243 (46)
1b dimer 683 (6) 625 (28)
monomer 343 (100)
229 (53)
569 (7)
511 (7)
455 (16)
1c dimer
763 (22) 685 (100) 609 (12)
229 (60)
monomer 381 (40) 305 (76)
a
m/z, relative intensity in parentheses.
Resu lts a n d Discu ssion
As starting material for the synthesis of tin com-
plexes, we selected lithium 2-lithiobenzenethiolate,
Li2(SC6H4), which can be obtained by reaction of ben-
zenethiolate and LiBu in a 1.2 ratio and isolated as a
white oil.11 It reacts smoothly with equimolecular
amounts of dialkyl- or diaryldihalotin(IV) complexes,
t
affording [{SnR2(SC6H4)}2] (R ) Me (1a ), Bu (1b), Ph
(1c)) as white solids (eq i, Scheme 1). Two different
formulations are possible for our complexes 1a -c, as
monomer with a five-atom metallacycle with the group
SC6H4 acting as a chelate group, or as a dinuclear
derivative with the orthometalated groups doubly bridg-
ing. The mass spectra (LSIMS+) of these compounds
show peaks corresponding to both protonated monomer
[SnR2(SC6H4) + H]+ and dimer [Sn2R4(SC6H4)2 + H]+,
with no peaks for higher nuclearities. Other peaks that
come from these monomers and dimers by the loss of
several organic groups (methyl, tert-butyl or phenyl)
(Table 1) are present. Although some associative pro-
cesses are not completely out of the question, the
elevated intensities of the dimer formulation and the
peaks that come from these suggest that these tin
complexes are dinuclear.
1
The H NMR spectra show signals corresponding to
inequivalent groups bonded to tin. In the methyl deriv-
ative (1a ), the presence of two signals from these groups
with the corresponding satellites from the active nuclei
of tin (119Sn and 117Sn) is the final proof for the dimer
formulation of complexes 1. In a monomer compound,
the organic groups have to be equivalent, but in
(12) Nakamoto, K. Infrared and Raman Spectra, 4th ed.; Wiley-
Interscience: New York, 1992, p 150.
(13) Gimeno, M. C.; J ones, P. G.; Laguna, A.; Laguna, M.; Terroba,
R. Inorg. Chem. 1994, 33, 3932.
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1996, 35, 2995.
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111, 654.
(15) Contel, M.; J ime´nez, J .; J ones, P. G.; Laguna, A.; Laguna, M.
J . Chem. Soc., Dalton Trans. 1994, 2515.

New Tin(IV) Dimers in Heteropolynuclear Synthesis
Organometallics, Vol. 16, No. 26, 1997 5639
Ta ble 2. Selected Bon d Len gth s (Å) a n d
An gles (d eg) for 2a
phorus trans to the S atom and the latter, at lower field,
to the one trans to the C atom. Complex 6 is one of the
few examples of ortho-metalated gold complexes.20
Au(1)-P(1)
Sn(1)-C(12)
Sn(1)-C(1)
S(1)-C(11)
2.259(3)
Au(1)-S(1)
Sn(1)-C(5)
Sn(1)-Cl(1)
2.306(3)
2.180(11)
2.442(3)
2.152(11)
2.185(12)
1.795(10)
Exp er im en ta l Section
P(1)-Au(1)-S(1)
C(12)-Sn(1)-C(1)
C(12)-Sn(1)-Cl(1)
C(1)-Sn(1)-Cl(1)
176.6(1) C(12)-Sn(1)-C(5)
122.3(4) C(5)-Sn(1)-C(1)
96.5(3) C(5)-Sn(1)-Cl(1)
113.8(4)
117.9(4)
100.2(4)
The starting materials Li2(SC6H4),11 [AuClL] (L ) PPh3,21
AsPh3,22 CH2PPh323), and PPN[AuCl2]24 were prepared as
described previously. All other reagents were commercially
available.
98.0(3) C(111)-P(1)-C(121) 107.3(5)
C(111)-P(1)-Au(1) 111.4(4) C(121)-P(1)-Au(1)
C(131)-P(1)-Au(1) 117.7(4) C(11)-S(1)-Au(1)
110.8(4)
98.7(3)
116.4(8)
107.7(9)
112.0(7)
108.0(8)
The C, H, N, S analyses were carried out on a Perkin-Elmer
2400 microanalyzer. Conductivities were measured in ap-
proximately 5 × 10-4 mol dm-3 acetone solutions with a
J enway 4010 conductimeter. The infrared spectra were
recorded (4000-200 cm-1) on a Perkin-Elmer 599 spectropho-
tometer, using Nujol mulls between polyethylene sheets. The
NMR spectra were recorded on a Bruker ARX 300 spectrom-
eter, in CDCl3. Chemical shifts are cited relative to SiMe4 (1H)
or 85% H3PO4 (external 31P). Mass spectra were recorded on
a VG Autospec LSIMS using 3-nitrobenzyl alcohol as matrix.
C(12)-C(11)-S(1)
C(13)-C(12)-Sn(1) 125.7(9) C(3)-C(1)-Sn(1)
C(2)-C(1)-Sn(1)
C(8)-C(5)-Sn(1)
C(7)-C(5)-Sn(1)
117.0(8) C(11)-C(12)-Sn(1)
108.1(8) C(4)-C(1)-Sn(1)
111.2(8) C(6)-C(5)-Sn(1)
109.9(8)
The Au-P bond length is 2.259(3) Å, very similar to
those found in [Au(SR)PPh3] (R ) Ph,16 2,4,6-C6H2(iPr)3,16
C17H15NSO217) derivatives, which lie in the range
2.2566(14)-2.260(3) Å. The Au-S distance is 2.306(3)
Å, in the range of the latter complexes [2.284(2)-
2.3229(13) Å]. The tin(IV) is tetracoordinated in an
irregular tetrahedral disposition, C(12)-Sn-C(5) )
113.8(4)°, C(12)-Sn-C(1) ) 122.3(4)°, C(5)-Sn-C(1) )
117.9(4)°, C(12)-Sn-Cl ) 96.5(3)°, C(5)-Sn-Cl )
100.2(3)°, and C(1)-Sn-Cl ) 98.0(3)°. The bond lengths
Sn-C are similar at ca. 2.17 Å, in accordance with
normal Sn(IV)-C distances.18 The is a short interaction
between the sulfur and the tin center (2.920 Å), which
can be resposible for the distorted geometry around this
metal, but there is no interaction between the tin and
the gold center (Sn‚‚‚Au ) 4.63 Å).
A tin-gold-tin trinuclear complex can be obtained
by this kind of process. The reaction of PPN[AuCl2] and
[{SnMe2(SC6H4)}2] in a 1:1 ratio gives the complex
PPN[Au{SnClMe2(SC6H4)}2] (5) (eq iv, Scheme 1). The
IR spectrum of the new trinuclear compound shows the
lack of the characteristic signal ν(Au-Cl), and in the
mass spectrum (LSIMS-) there is a peak corresponding
to the anion [M - PPN]- at m/z 781 (85%). The acetone
solution of this complex shows a conductivity value, 124
Ω-1 cm2 mol-1, in agreement with a formulation as a
1:1 electrolyte.19
It is noteworthy that the mass spectra of 2a -c show
a signal at m/z 1026 asignable to an [Au2(SC6H4)(PPh3)2]+
ion. Complexes of this kind could be obtained if the
transfer of the SC6H4 ligand was complete from the tin
to the gold centers. So we tried the reaction between
2a -c with [AuCl(PPh3)] in a 1:1 ratio in chloroform at
reflux with the presence of catalytic amounts of
[PtCl2(NCPh)2], but no reaction occurred. [Au2(SC6H4)-
(PPh3)2] (6) can be obtained by reaction of the ortholithi-
ated thiophenol with [AuCl(PPh3)] in a 1:2 ratio. Com-
plex 6 shows in the mass spectrum the parent peak at
m/z 1026 (12%), and the 31P{1H} NMR spectrum shows,
at room temperature, two sharp singlets at 37.2 and
41.5 ppm. The former could be assigned to the phos-
t
Syn th esis of [{Sn R2(SC6H4)}2] [R ) Me (1a ), Bu (1b),
P h (1c)]. Lithium 2-lithiobenzenethiolate was prepared as
described previously from thiophenol (0.788 g, 7.2 mmol),
TMDA (2.38 cm3, 15.9 mmol), and n-butyllithium (1.015 g, 15.9
mmol). Solid Li2(SC6H4) was isolated by filtration under
nitrogen, washed with dry hexane (2 × 15 cm3), and dissolved
in dry THF (10 cm3) precooled to -78 °C. The solution was
then treated dropwise during 45 min with [SnCl2R2] [R ) Me
t
(1.090g, 5 mmol), Bu (1.519 g, 5 mmol), Ph (1.719 g, 5mmol)]
dissolved in dry THF (15 cm3). The mixture was warmed to
room temperature overnight; the solution was acidified with
dilute chloridic acid and then concentrated in vacuum, and
the residue was taken up in dichloromethane. The solution
was washed with water and dried with MgSO4 and active
carbon, the solvent was evaporated to 5 cm3, and hexane (20
cm3) was added, resulting in the precipitation of white
complexes. Yield (%): 58 (1a ), 74 (1b), 47 (1c).
Data for 1a are as follows. Anal. Calcd: C, 37.4; H, 3.9; S,
12.5. Found: C, 36.85; H, 3.8; S, 11.85. ΛM: 4 Ω-1 cm2 mol-1
.
2
1H NMR: δ ) 7.50 and 7.24 (m, 8H, SC6H4), 0.45 (s, J Sn-H
)
2
57.1 Hz, 3H, Me) 0.41 (s, J Sn-H ) 51.6 Hz, 3H, Me).
Data for 1b are as follows. Anal. Calcd: C, 49.3; H, 6.5; S,
9.4. Found: C, 49.3; H, 6.05; S, 8.8. ΛM: 4 Ω-1 cm2 mol-1. 1H
NMR: δ ) 7.77, 7.32, 7.13, and 7.07 (m, 8H, SC6H4), 1.35 (s,
t
3J Sn-H ) 40.3 Hz, 18H, Bu).
Data for 1c are as follows. Anal. Calcd: C, 56.75; H, 3.7;
S, 8.4. Found: C, 56.25; H, 3.65; S, 8.1. ΛM: 3 Ω-1 cm2 mol-1
.
1H NMR: δ ) 7.86-6.88 (m, 28H, SC6H4 and Ph).
Syn th esis of [Au Sn ClR2(SC6H4)L] [R ) Me, L ) P P h 3
t
(2a ), AsP h 3 (3a ), CH2P P h 3 (4a ); R ) Bu L ) P P h 3 (2b),
AsP h 3 (3b), CH2P P h 3 (4b); R ) P h , L ) P P h 3 (2c), AsP h 3
(3c), CH2P P h 3 (4c)]. To a dichloromethane solution (20 cm3)
of 1a (0.026 g, 0.1 mmol), 1b (0.034 g, 0.1 mmol), or 1c (0.038
g, 0.1 mmol) was added [AuClL] [L ) PPh3 (0.049 g, 0.1 mmol),
AsPh3 (0.054 g, 0.1 mmol), or CH2PPh3 (0.051 g, 0.1 mmol)].
After 1 h of stirring, the solutions were concentrated in vacuo,
and the addition of hexane afforded the precipitation of the
new complexes as white, pale yellow (3a , 4c), or pink solids
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5640 Organometallics, Vol. 16, No. 26, 1997
Ferna´ndez et al.
(4b). Yield (%): 75 (2a ), 48 (3a ), 67 (4a ), 82 (2b), 49 (3b), 68
(4b), 71 (2c), 51 (3c), 62 (4c).
nol (0.788 g, 7.2 mmol), TMDA (2.38 cm3, 15.9 mmol), and
n-butyllithium (1.015 g, 15.9 mmol). Solid Li2(SC6H4) was
isolated by filtration under nitrogen, washed with dry hexane
(2 × 15 cm3), and dissolved in dry THF (40 cm3) precooled to
-78 °C. Then [AuCl(PPh3)] (4.947 g, 10 mmol) was added
slowly. The mixture was warmed to room temperature
overnight; the solution was acidified with dilute chloridic acid
and then was concentrated in vacuum, and the residue was
taken up in dichloromethane. The solution was washed with
water and dried with MgSO4 and active carbon; evaporation
of the solvent to 5 cm3 and addition of diethyl ether (20 cm3)
resulted in the precipitation of white complex. Anal. Calcd:
C, 49.15; H, 3.35; S, 3.1. Found: C, 49.7; H, 3.35; S, 3.2. ΛM:
Data for 2a are as follows. Anal. Calcd: C, 41.55; H, 3.35;
S, 4.25. Found: C, 41.35; H, 3.25; S, 3.95. ΛM: 3 Ω-1 cm2
mol-1 31P{1H} NMR: δ ) 37.9 (s). 1H NMR: δ ) 7.69 and
.
7.20 (m, 4H, SC6H4), 7.52-7.44 (m, 15H, PPh3), 0.96 (s, 2J Sn-H
) 65.3 Hz, 6H, Me). Mass spectrum, m/z (relative intensity):
[M - Cl]+ ) 717 (35), [M - R]+ ) 737 (19).
Data for 3a are as follows. Anal. Calcd: C, 39.25; H, 3.15;
S, 4.05. Found: C, 39.0; H, 2.9; S, 4.15. ΛM: 7 Ω-1 cm2 mol-1
.
1H NMR: δ ) 7.68 and 7.20 (m, 4H, SC6H4), 7.43 (m, 15H,
2
AsPh3), 0.97 (s, J Sn-H ) 63.6 Hz, 6H, Me). Mass spectrum,
m/z (relative intensity): [M - Cl]+ ) 761 (59), [M - R]+
782 (30).
)
4 Ω-1 cm2 mol-1 1H NMR: δ ) 7.76, 7.09, 6.99, and 6.84 (m,
.
Data for 4a are as follows. Anal. Calcd: C, 42.35; H, 3.55;
4H, SC6H4), 7.61-7.32 (m, 30H, PPh3).
S, 4.2. Found: C, 42.0; H, 3.4; S, 3.9. ΛM: 37 Ω-1 cm2 mol-1
.
X-r a y d eter m in a tion of [Au Sn Cl(tBu )2(SC6H4)(P P h 3)].
Single crystals were grown by diffusing hexane into a dichlo-
romethane solution of 2a at room temperature. A colorless
prism 0.18 mm × 0.16 mm × 0.16 mm was used. The
diffraction experiments were carried out on a Delft Instru-
ments FAST TV area detector diffractometer positioned at the
window of a rotating-anode generator and using Mo KR
radiation (λ ) 0.710 69 Å) at 150 K, following procedures
described elsewhere.25 In total, 12 761 reflections were col-
lected in the θ range 1.96-25.10° (-11 e h e0, -12 e k e0,
-30 e l e 0; 0 e h e11, 0 e k e12, 0 e l e 25). The structure
was determined using the PATT instruction of SHELXS
86,26refined by full-matrix least-squares on Fo2, using the
program SHELXL 93.27 Unfortunately, no additional ψ data
were collected, and, due to the high absortion coefficient, all
data used were corrected for Lorentz-polarization factors, and
subsequently for absorption (µ ) 5.6 mm-1), using the program
DIFABS.28 For Z ) 4, we found an orthorhombic system [a )
10.0780(10) Å, b ) 11.1730(10) Å, c ) 28.167(2) Å] and space
group P212121. The non-hydrogen atoms were refined with
anisotropic thermal parameters. All hydrogen atoms were
included in idealized positions. Refinement proceeds to R )
0.0310, wR ) 0.0964, and the goodness of fit on F2 was 1.054
for 4852 data and 340 parameters, and R ) 0.0382, wR )
0.0974 for all data. In the final Fourier synthesis, the electron
31P{1H} NMR: δ ) 30.7 (s). 1H NMR: δ ) 7.63-7.47 (m, 15H,
2
-PPh3), 7.11 and 7.01 (m, 4H, SC6H4), 1.95 (d, J P-H ) 12.2
2
Hz, 2H, -CH2-), 0.96 (s, J Sn-H ) 65.1 Hz, 6H, Me). Mass
spectrum, m/z (relative intensity): [M - Cl]+ ) 729 (31),
[M - R]+ ) 749 (30).
Data for 2b are as follows. Anal. Calcd: C, 46.0; H, 4.45;
S, 3.85. Found: C, 45.9; H, 4.35; S, 3.7. ΛM: 2 Ω-1 cm2 mol-1
.
31P{1H} NMR: δ ) 37.4 (s). 1H NMR: δ ) 7.77 and 7.13 (m,
2
4H, SC6H4), 7.49-7.46 (m, 15H, PPh3), 1.46 (s, J Sn-H ) 52.6
t
Hz, 18, Bu). Mass spectrum, m/z (relative intensity): [M -
Cl]+ ) 801 (27), [M - R]+ ) 779 (15).
Data for 3b are as follows. Anal. Calcd: C, 43.7; H, 4.25;
S, 3.65. Found: C, 43.15; H, 4.4; S, 4.0. ΛM: 7 Ω-1 cm2 mol-1
.
1H NMR: δ ) 7.74 and 7.13 (m, 4H, SC6H4), 7.57-7.46 (m,
3
15H, AsPh3), 1.46 (s, J Sn-H ) 48.8 Hz, 18, tBu). Mass
spectrum, m/z (relative intensity): [M - R]+ ) 846 (11).
Data for 4b are as follows. Anal. Calcd: C, 46.65; H, 4.65;
S, 3.75. Found: C, 46.35; H, 4.25; S, 3.7. ΛM: 36 Ω-1 cm2
mol-1
.
31P{1H} NMR: δ ) 30.5 (s). 1H NMR: δ ) 7.69-7.47
2
(m, 15H, -PPh3), 7.00 and 6.90 (m, 4H, SC6H4), 1.98 (d, J P-H
) 12.2 Hz, 2H, -CH2-), 1.35 (s, 3J Sn-H ) 52.5 Hz, 18, tBu). Mass
spectrum, m/z (relative intensity): [M - Cl]+ ) 815(47), [M -
R]+ ) 793(9).
Data for 2c are as follows. Anal. Calcd: C, 49.35; H, 3.35;
S, 3.65. Found: C, 49.35; H, 3.35; S, 3.5. ΛM: 2 Ω-1 cm2 mol-1
.
density fluctuates in the range 1.196 to -0.622 e Å-3
.
31P{1H} NMR: δ ) 37.4( s). 1H NMR: δ ) 8.07-7.22 (m, 29H).
Mass spectrum, m/z (relative intensity): [M - Cl]+ ) 842 (28),
[M - R]+ ) 800 (16).
Ack n ow led gm en t. The Spanish authors thank the
Direccio´n General de Investigacio´n Cient´ıfica y Te´cnica
(Grant PB95-0140) for financial support and Ministerio
de Educacio´n y Cultura for a grant (to R.T.), and M.B.H.
thanks the Engineering and Physical Sciences Research
Committee for support of the X-ray facilities.
Data for 3c are as follows. Anal. Calcd: C, 47.0; H, 3.2; S,
3.5. Found: C, 46.75; H, 2.65; S, 3.85. ΛM: 3 Ω-1 cm2 mol-1
.
1H NMR: δ ) 8.05-6.90 (m, 29H). Mass spectrum, m/z
(relative intensity): [M - Cl]+ ) 885 (51), [M - R]+ ) 843
(41). Data for 4c are as follows. Anal. Calcd: C, 49.95; H,
3.4; S, 3.6. Found: C, 49.55; H, 3.45; S, 3.4. ΛM: 49 Ω-1 cm2
Su p p or tin g In for m a tion Ava ila ble: Description of the
crystal structure determinations, including tables of crystal
data, data collection, and solution and refinement parameters,
hydrogen coordinates, bond distances and angles, and thermal
parameters (5 pages). Ordering information is given on any
current masthead page.
mol-1 31P{1H} NMR: δ ) 30.7 (s). 1H NMR: δ ) 8.04-6.99
.
(m, 29H), 1.73 (d, 2J P-H ) 12.0 Hz, 2H, -CH2-). Mass spectrum,
m/z(relative intensity): [M - Cl]+ ) 855 (20), [M - R]+ ) 813
(12).
Syn th esis of [Au {Sn ClMe2(SC6H4)}2] (5). To a dichlo-
romethane solution (20 cm3) of 1a (0.026 g, 0.1 mmol) was
added PPN[AuCl2] (0.040 g, 0.05 mmol). After 1 h of stirring,
the solution was concentrated in vacuum, and the addition of
hexane afforded the precipitation of the new complex as a
white solid. Yield: 43%. Anal. Calcd: C, 47.3; H, 3.8; S, 4.85.
OM970326P
(25) Danopoulos, A. A.; Wilkinson, G.; Hussain-Bates, B.; Hurst-
house, M. B. J . Chem. Soc., Dalton Trans. 1991, 1855.
(26) Sheldrick, G. M. SHELXS 86. Acta Crystallogr., Sect. A 1990,
46, 467.
(27) Sheldrick, G. M. SHELXL 93, Program for Crystal Structure
Refinement. University of Go¨tingen, 1993.
(28) Walker, N. P. C.; Stuart, D. Acta Crystallogr., Sect. A. 1983,
39, 158 (adapted for FAST geometry by Karaulov A., University of
Wales, Cardiff, 1991).
Found: C, 47.7; H, 4.2; S, 5.15. ΛM: 117 Ω-1 cm2 mol-1 1H
.
NMR: δ ) 7.64-7.42 and 7.04 (m, 8H, SC6H4), 0.88 (s, 2J Sn-H
) 65.6 Hz, 12H, Me).
Syn th esis of [Au 2(SC6H4)(P P h 3)2] (6). Lithium 2-lithioben-
zenethiolate was prepared as described previously from thiophe-