Diorganotin(IV) derivatives of arenephosphinothiol ligands. The crystal structure of [Ph2Sn{2-(Ph2P)C6H4S}2] and [Me2Sn{2-(Ph2PO)-6-(Me3Si)C6H 3S

Article abstract of DOI:10.1016/S0022-328X(99)00568-9

The diorganotin complexes, [Me₂Sn{2-(Ph₂P)C₆H₄S}₂] (1), [Ph₂Sn{2-(Ph₂P)C₆H₄S}₂] (2), [Me₂Sn{2-(Ph₂PO)-6-(Me₃Si)C

Full text of DOI:10.1016/S0022-328X(99)00568-9

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 595 (2000) 59–65
Diorganotin(IV) derivatives of arenephosphinothiol ligands. The
crystal structure of [Ph2Sn{2-(Ph2P)C6H4S}2] and
[Me2Sn{2-(Ph2PO)-6-(Me3Si)C6H3S}2]
P. Pe´rez-Lourido a, J. Romero b,*, J.A. Garc´ıa-Va´zquez b, A. Sousa b,1, J. Zubieta c,
U. Russo d
a Departamento de Qu´ımica Inorga´nica, Uni6ersidad de Vigo, Ponte6edra, Spain
b Departamento de Qu´ımica Inorga´nica, Facultad de Qu´ımica, Uni6ersidad de Santiago de Compostela, E-15706 Santiago de Compostela,
Galicia, Spain
c Department of Chemistry, Syracuse Uni6ersity, Syracuse, NY 13244, USA
d Dipartimento di Chimica Inorganica, Metallorganica e Analitica, Uni6ersita´ de Padua, Padua, Italy
Received 12 July 1999; received in revised form 17 September 1999
Abstract
The diorganotin complexes, [Me2Sn{2-(Ph2P)C6H4S}2] (1), [Ph2Sn{2-(Ph2P)C6H4S}2] (2), [Me2Sn{2-(Ph2PO)-6-(Me3Si)C6H3S}2]
(3) and [Ph2Sn{2-(Ph2PO)-6-(Me3Si)C6H3S}2] (4), have been prepared by reacting the corresponding diorganotin(IV) chloride with
2-(Ph2P)C6H4SH and 2-(Ph2PO)-6-(Me3Si)C6H3SH. Compound 2 crystallises in the monoclinic space group and the tin atom is
tetrahedrally coordinated to two ligands acting as monodentate through the thiolate sulphur atoms. Compound 3 also crystallises
in the monoclinic space group and, in this compound, the tin atom is octahedrically coordinated [SnC2O2S2]. Spectral data for the
complexes (IR, NMR, FAB and Mo¨ssbauer spectra) are discussed and related to the structural information. © 2000 Elsevier
Science S.A. All rights reserved.
Keywords: Organotin complexes; Tin complexes; Phosphinothiolate complexes; Crystal structure
1. Introduction
interaction of main group metals with thiolate ligands,
we report on the synthesis and characterisation of
complexes of dimethyl and diphenyltin(IV) with
arenephosphinothiol ligands incorporating both thio-
late sulphur and tertiary phosphorous atoms as donor
groups. The crystal structures of [Ph2Sn{2-
(Ph2P)C6H4S}2] and [Me2Sn{2-(Ph2PO)-6-(Me3Si)C6H3-
S}2] are also reported.
Interest in the coordination chemistry of metal–sul-
phur complexes arises from their potential relevance to
active sites in metalloenzymes and also from their abil-
ity to adopt various nuclearities and significant struc-
tural complexity [1–3]. In addition, interaction of toxic
main group metals with biological systems frequently
involves bonding to enzyme sulfhydryl groups and
main group metal complexes are of some interest in the
design of detoxification reagents [4]. This interest has
led us to study organotin compounds that in a biologi-
cal medium react with thiol groups in relevant
molecules, yielding products characterised by SnꢀS
bonds. As a result of our continuing interest in the
2. Experimental
All manipulations were carried under an inert atmo-
sphere of dry nitrogen. Dimethyltin dichloride and
diphenyltin dichloride (Aldrich) were used as supplied.
Syntheses of ligands were carried out using standard
literature procedures with some minor modifications
[4]. Elemental analyses were performed in a Carlo–
Erba EA 1108 microanalyser. IR spectra were recorded
in KBr disks using a Bruker IFS 66V spectrophotome-
* Corresponding author. Fax: +34-981-594-921.
E-mail addresses: qiromero@uscmail.usc.es (J. Romero), qian-
soal@uscmail.usc.es (A. Sousa)
1 Also corresponding author.
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00568-9

60
P. Pe´rez-Lourido et al. / Journal of Organometallic Chemistry 595 (2000) 59–65
ter. 1H- and 31P-NMR spectra were recorded on a
Bruker AMX300 MHz instrument using CDCl3 as sol-
vent. H chemical shifts were determined against TMS
evaporated to give white crystals suitable for X-ray
studies (0.14 g, 78%). M.p.: 190°C. Anal. Calc. for
C44H50P2O2S2Si2Sn (mol. wt. 911): C, 57.96; H, 5.49; S,
7.02. Found: C, 57.75; H, 5.49; S, 6.99%. IR (KBr,
cm−1): 2939(m), 2740(m), 2677(s), 2491(m), 1545(m),
1475(m), 1436(m), 1357(m), 1131(s), 1044(m), 852(s),
1
and 31P chemical shifts against 85% H3PO4 as internal
standard. 119Sn-NMR spectra were recorded on a
Bruker AMX500 instrument and referred to Me4Sn as
external reference. The mass spectra were recorded on a
Kratos MS50TC spectrophotometer connected to a
DS90 data system, using 3-nitrobenzyl alcohol (3-NBA)
1
794(m), 695(s), 556(s). H-NMR (CDCl3, ppm): l 7.8–
6.5 (m, 26H), 1.0 (s, 6H), 0.5 (s, 9H), 0.4 (s, 9H).
13C-NMR (CDCl3, ppm): l 150–123, 8.5(s), 0.01(s),
−0.01(s). 31P-NMR (CDCl3, ppm): l 38.8, 35.1. 119Sn-
NMR (CDCl3, ppm): l −93.
a
matrix material. The Mo¨ssbauer spectra were
recorded at 80 K on a constant acceleration apparatus
with a Ca119SnO3 source.
2.4. Synthesis of [Ph2Sn{2-(Ph2PO)-6-(Me3Si)-
C6H3S}2] (4)
2.1. Synthesis of [Me2Sn{2-(Ph2P)C6H4S}2] (1)
A solution containing 0.067 g (0.196 mmol) of
diphenyltin dichloride, 0.15 g (0.393 mmol) of 2-
To a refluxing solution of 2-(Ph2P)C6H4SH (0.200 g,
0.680 mmol) in 50 ml of methanol was added a solution
of dimethyltin dichloride (0.075 g, 0.340 mmol) in 15 ml
of methanol. To the mixture NEt3 (0.071 g, 0.700
mmol) was added. The solution was stirred at room
temperature (r.t.) for 4 h, filtered and evaporated to
give a white crystalline solid (0.212 g, 85%). M.p.: 99°C.
Anal. Calc. for C38H34P2S2Sn (mol. wt. 735): C, 62.04;
H, 4.62; S, 8.70. Found: C, 61.56; H, 4.62; S, 8.62%. IR
(KBr, cm−1): 3050(m), 2938(m), 2678(m), 1570(m),
1477(m), 1433(m), 1249(w), 1099(m), 748(s), 696(s),
diphenylphosphinyl-6-trimethylsilylbenzenethiol
and
0.040 g (0.400 mmol) of triethylamine in 30 ml of
methanol was refluxed for 3 h. The resulting solution
was evaporated to give white needles (0.17 g, 84%).
M.p.: 245°C. Anal. Calc. for C54H54P2O2S2Si2Sn (mol.
wt. 1035): C, 62.61; H, 5.22; S, 6.17. Found: C, 62.19;
H, 5.29; S, 6.13%. IR (KBr, cm−1): 2941(m), 2678(m),
2492(m), 1545(m), 1437(m), 1357(m), 1133(s), 1048(m),
1
852(s), 729(m), 694 (s), 556(s). H-NMR (CDCl3, ppm):
1
l 8.1–6.5 (m, 36H), 0.4 (s, 9H), 0.3 (s, 9H). 13C-NMR
(CDCl3, ppm): l 150–123, 0.09(s), −0.01(s). 31P-NMR
(CDCl3, ppm): l 41.5, 35.2. 119Sn-NMR (CDCl3, ppm):
l −260.
506(s). H-NMR (CDCl3, ppm): l 7.9–6.6 (m, 28H),
0.9 (s, 6H). 13C-NMR (CDCl3, ppm): l 143–125, 8.6(s).
31P-NMR (CDCl3, ppm):
l
−14.0. 119Sn-NMR
(CDCl3, ppm): l 75.
2.2. Synthesis of [Ph2Sn{2-(Ph2P)C6H4S}2] (2)
Table 1
The same procedure was used for the synthesis of the
diphenyltin derivative as that described for 1. A solu-
tion of Ph2SnCl2 (0.117 g, 0.340 mmol), 2-
(Ph2P)C6H4SH (0.200 g, 0.680 mmol) and NEt3 (0.071g,
0.700 mmol) in 40 ml of methanol was refluxed for 3 h.
The solution was concentrated to give monocrystals
suitable for X-ray studies. (0.236 g, 81%). M.p.: 180°C.
Anal. Calc. for C48H38P2S2Sn (mol. wt. 859): C, 67.05;
H, 4.42; S, 7.45. Found: C, 67.06; H, 4.26; S, 7.38%. IR
(KBr, cm−1): 1573(m), 1479(m), 1433(s), 1250(w),
1098(m), 745(s), 695(s), 508(s). 1H-NMR (CDCl3,
ppm): l 7.9–6.5 (m). 13C-NMR (CDCl3, ppm): l 142–
126. 31P-NMR (CDCl3, ppm): l −15.3. 119Sn-NMR
(CDCl3, ppm): l −60.
Crystallographic data for [Ph2Sn{2-(Ph2P)C6H3S}2] (2) and
[Me2Sn{2-(Ph2PO)-6-(Me3Si)C6H3S}2] (3)
2
3
Chemical formula
Molecular weight
Temperature (K)
Wavelength (A)
Crystalline system
Space group
C48H38P2S2Sn
859.53
293(2)
0.71073
Monoclinic
P21/n
C44H50P2O2S2Si2Sn
911.85
293(2)
0.71073
Monoclinic
P21/c
,
Cell constants
,
a (A)
18.8213(3)
9.7058(2)
23.84480(10)
107.233(2)
4160.32(11)
4
10.0595(2)
19.1870(4)
23.9621(4)
95.390(1)
4604.5(2)
4
,
b (A)
,
c (A)
i (°)
3
,
V (A )
Z
2.3. Synthesis of [Me2Sn{2-(Ph2PO)-6-(Me3Si)-
C6H3S}2] (3)
Absorption coefficient
0.824
0.801
(mm−1
)
Size (mm)
0.15×0.10×0.08 0.30×0.20×0.15
Collected reflections
Independent reflections 9688
R
Rw
25117
29138
10890
0.0436
0.1086
A solution of Me2SnCl2 (0.043 g, 0.196 mmol), 2-
(Ph2PO)-6-(Me3Si)C6H3SH (0.150 g, 0.393 mmol) and
NEt3 (0.040g, 0.400 mmol) in 30 ml of methanol was
stirred and refluxed for 4 h. The resulting solution was
0.0602
0.1065

P. Pe´rez-Lourido et al. / Journal of Organometallic Chemistry 595 (2000) 59–65
61
Table 2
2.5. X-ray crystallography
4
,
3
Atomic coordinates (A×10 ) and equivalent isotropic displacement
parameters (A ×10 ) for [Ph2Sn{2-(Ph2P)C6H4S}2] (2)
2
,
Compounds 2 and 3 were studied on a Siemens
SMART system using graphite monochromated Mo–Ka
x
y
z
Ueq
,
radiation (u=0.71073 A). All data collections were
Sn(1)
S(1)
S(2)
P(1)
P(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
9627(1)
8001(1)
9071(1)
2242(1)
1264(1)
2626(1)
1304(1)
3684(1)
2330(2)
2664(2)
2736(3)
2483(3)
2155(2)
2069(2)
2596(2)
2602(3)
2810(3)
3025(4)
3037(3)
2811(2)
757(2)
25(1)
37(1)
29(1)
29(1)
26(1)
28(1)
36(1)
49(2)
54(2)
48(2)
34(1)
33(1)
50(2)
82(3)
98(3)
88(3)
55(2)
32(1)
31(1)
38(1)
44(1)
45(1)
40(1)
32(1)
34(1)
38(1)
48(2)
58(2)
47(2)
29(1)
41(1)
56(2)
60(2)
54(2)
42(1)
26(1)
25(1)
33(1)
41(1)
39(1)
34(1)
27(1)
40(1)
52(2)
53(2)
51(2)
41(1)
28(1)
32(1)
40(1)
48(2)
47(2)
37(1)
carried out at r.t. The crystal parameters and other
experimental details of the data collection are summa-
rized in Table 1. A complete description of the details
of the crystallographic methods is given in the Section
4. The structures were solved by direct methods [5].
Neutral atomic scattering factors were taken from
Cromer and Waber [6] and anomalous dispersion cor-
rections were taken from those of Creagh and McAuley
[7]. All calculations were performed using SHELXTL [8]
for compound 3 and SHELXL-97 [9] for compound 2.
Non-hydrogen atoms were refined anisotropically. No
anomalies were encountered in the refinements of any
of the structures. Atomic positional parameters and
isotropic temperature factors for the structures are pre-
sented in Tables 2 and 3.
9035(1)
9239(1)
9997(1)
9804(1)
8902(3)
9143(3)
8631(4)
7874(4)
7630(3)
8145(3)
10814(2)
11190(3)
11964(4)
12351(4)
12000(4)
11214(3)
8695(3)
9100(3)
8787(3)
8105(3)
7712(3)
8004(3)
10223(3)
10705(3)
10845(3)
10508(4)
10020(4)
9884(4)
10659(3)
11407(3)
11925(3)
11709(4)
10976(3)
10454(3)
9988(2)
10228(2)
10815(3)
11160(3)
10918(3)
10338(3)
10310(2)
10196(3)
10576(3)
11075(3)
11197(3)
10818(3)
8897(2)
8366(3)
7683(3)
7527(3)
8047(3)
8733(3)
10188(1)
6309(1)
8024(1)
6378(5)
5191(5)
4219(6)
4459(7)
5621(7)
6561(6)
8044(6)
9284(7)
9328(11)
8159(14)
6907(12)
6855(8)
7702(5)
6498(5)
5477(6)
5695(7)
6907(7)
7901(6)
4493(5)
3981(5)
2584(5)
1663(6)
2157(6)
3550(6)
7225(5)
7272(6)
7963(7)
8624(7)
8596(7)
7900(6)
10619(5)
9742(5)
10180(5)
11445(6)
12309(5)
11903(5)
7167(5)
7436(6)
6719(7)
5717(6)
5408(6)
6131.(S)
8313(5)
7279(5)
7365(6)
8507(7)
9561(7)
9477(6)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(37)
C(38)
C(39)
C(40)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
C(47)
C(48)
742(2)
315(2)
−95(2)
−91(2)
337(2)
1266(2)
970(2)
3. Results and discussion
The reactions between Me2SnCl2, Ph2SnCl2 and the
arenephosphinothiol ligands, [RPꢀSH], lead to white air
stable crystalline compounds, whose analytical data are
concordant with a general formulation [R2Sn(RPꢀS)2].
953(2)
1242(2)
1535(3)
1552(2)
1002(2)
1342(2)
1137(3)
598(3)
3.1. Crystal structure of [Ph2Sn{2-(Ph2P)C6H4S}2] (2)
The crystal structure of [Ph2Sn{2-(Ph2P)C6H3S}2] is
shown in Fig. 1, together with the atomic numbering
scheme. Selected bond distances and angles are in Table
4. The compound consists of discrete molecules with
the tin atom bonded to two carbon atoms from the
phenyl groups and two sulphur atoms from two
monoanionic ligands. The phosphorus atoms do not
interact with the metal. It is tempting to speculate that
the steric hindrance produced by the phenyl groups
precludes bidentate coordination by the ligand.
The environment around the tin atom is tetrahedrally
distorted with bond angles around the metal of
126.7(2)°, CꢀSnꢀC, and 83.74(4)°, S(2)ꢀSnꢀS(1), in both
cases far from those expected for the idealized values.
The SnꢀS bond distances (2.5034(12) and 2.4941(13) A)
are close to the sum of covalent radii (2.42 A) [10].
263(3)
464(2)
3256(2)
3750(2)
4229(2)
4236(2)
3747(2)
3266(2)
4374(2)
4916(2)
5415(2)
5388(3)
4855(3)
4351(2)
3815(2)
3642(2)
3760(2)
4049(2)
4215(2)
4100(2)
,
,
3.2. Crystal structure of [Me2Sn{2-(Ph2PO)6-
(Me3Si)C6H3S}2] (3)
The molecular structure of [Me2Sn{2-(Ph2PO)-6-
(Me3Si)C6H3S}2] is shown in Fig. 2. A selection of bond
distances and angles are shown in Table 5. In this
compound the tin atom is in a distorted octahedral
environment coordinated by two methyl groups and
two monoanionic bidentate ligands, which coordinate
to the metal through the thiolato sulphur and the
oxygen atoms.
The four donor atoms of the two ligands are located
in equatorial positions with the S2O2 grouping deviat-

62
P. Pe´rez-Lourido et al. / Journal of Organometallic Chemistry 595 (2000) 59–65
,
ing from planarity, O(1) and S(2) 0.024 A above and
theoretical value (180°). The two methyl groups are
trans to each other, with a MeꢀSnꢀMe bond angle of
152.8(2)°. The deviation from the regular geometry is
probably due to steric hindrance produced by the
trimethylsilyl groups.
,
S(1) and O(2) 0.023 A below the best plane defined by
the donor atoms. The oxygen atoms are in a cis ar-
rangement. The bond angles involving atoms trans to
each other (173.90(5) and 172.89(6)°) are close to the
The SnꢀS bond distances in the compound (2.5627(8)
Table 3
,
and 2.5513(8) A) are slightly higher than the sum of the
4
,
3
Atomic coordinates (A×10 ) and equivalent isotropic displacement
parameters (A ×10 ) for [Me2Sn{2-(Ph2PO)6-(Me3Si)C6H3S}2] (3)
,
covalent radii for the tin and sulphur atoms (2.42 A)
2
,
and similar to those found in other hexacoordinate
organotin compounds containing thiolate ligands.
Thus, the values do not differ much from those found
x
y
z
Ueq
Sn(1)
S(1)
S(2)
P(1)
P(2)
Si(1)
Si(2)
O(1)
O(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
2755(1)
3079(1)
3611(1)
1436(1)
3165(1)
1816(1)
6559(1)
1910(2)
2556(2)
693(3)
4496(4)
1443(3)
706(3)
−588(4)
−1146(4)
−414(4)
890(3)
4962(1)
4172(1)
4012(1)
5523(1)
5366(1)
2577(1)
3239(1)
5751(1)
5628(1)
4831(2)
5576(2)
4072(2)
4658(2)
4572(2)
3914(2)
3339(2)
3398(2)
2478(2)
1820(2)
2541(2)
6114(2)
6250(2)
6695(2)
7007(3)
6878(4)
6438(3)
5555(2)
5166(3)
5281(3)
5770(3)
6143(3)
6042(2)
4406(2)
5008(2)
5336(2)
5062(2)
4450(2)
4105(2)
3003(3)
3269(3)
2555(2)
4730(2)
4761(2)
4296(2)
3803(2)
3774(2)
4229(2)
6075(2)
6750(2)
7294(2)
7171(2)
6504(2)
5957(2)
2560(1)
3419(1)
1932(1)
3791(1)
1163(1)
3475(1)
2130(1)
3243(1)
1672(1)
2314(1)
2728(2)
3627(1)
3784(1)
3931(1)
3937(2)
3800(2)
3643(1)
3968(2)
3575(2)
2732(2)
3986(1)
4537(2)
4666(2)
4245(2)
3696(2)
3568(2)
4370(1)
4853(2)
5318(2)
5298(2)
4820(3)
4351(2)
1649(1)
1310(1)
1113(1)
1240(2)
1549(2)
1760(1)
2115(3)
2877(2)
1724(2)
772(1)
24(1)
27(1)
25(1)
27(1)
22(1)
31(1)
41(1)
33(1)
28(1)
35(1)
39(1)
26(1)
27(1)
35(1)
39(1)
35(1)
28(1)
46(1)
46(1)
43(1)
32(1)
47(1)
54(1)
55(1)
85(2)
65(2)
34(1)
48(1)
68(2)
79(2)
76(2)
54(1)
23(1)
23(1)
28(1)
35(1)
33(1)
27(1)
77(2)
61(1)
60(1)
24(1)
32(1)
42(1)
45(1)
43(1)
31(1)
25(1)
36(1)
48(1)
45(1)
40(1)
33(1)
,
in [Me2Sn(pyt)2] (2.487 A) [11], where pyt stands for
pyridine-2-thiolate. On the other hand, the bond dis-
,
tances SnꢀC (2.118(3) and 2.117(3) A) are characteristic
of [R2Sn(bidentate)2] complexes [12].
3.3. IR spectra
The IR spectra of these complexes do not show the
band associated with w(SꢀH), which in the free ligands
appears in the range 2550–2400 cm−1. This is indica-
tive of the anionic form of the ligand in the complexes.
In the case of the complexes containing the ligand
2-(Ph2PO)-6-(Me3Si)C6H3SH, the spectra also show in-
tense bands at 855–840 and 1130–1125 cm−1 due to
w(SiꢀC) and w(PꢁO), respectively.
C(9)
3361(4)
691(4)
2207(4)
156(4)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(37)
C(38)
C(39)
C(40)
C(41)
C(42)
C(43)
C(44)
3.4. NMR spectra
−67(4)
−1083(5)
−1875(5)
−1663(6)
−646(5)
2706(4)
2621(4)
3544(5)
4518(6)
4619(6)
3721(5)
4987(3)
4814(3)
5919(3)
7186(3)
7350(3)
6271(3)
8364(5)
6186(5)
5548(5)
2142(3)
764(3)
In all cases, the 1H-NMR spectra show that the
signal due to the SꢀH group, which in the free ligands
appears at about l 4.1 ppm is absent. This confirms the
IR conclusion that the ligands are in the anionic form
1
in the complexes. The H-NMR spectrum of [Me2Sn{2-
(Ph2P)C6H4S}2] shows a signal at l 0.9 ppm (6H) as a
1
singlet, accompanied by satellites due to the H–119Sn
coupling that corresponds to the hydrogen atoms of the
methyl of the Me2Sn moiety. The 13C-NMR spectrum
shows the signal of the methyl groups at l 8.6 ppm.
The 31P spectrum displays a signal at −14.0 ppm, the
same position as that of the free ligand. This shows
that, in solution, the phosphorous atoms are not coor-
dinated to the metal. On the other hand, the 119Sn-
NMR spectrum shows a signal at l 75 ppm, a value in
the range found for tetrahedral complexes of tin, and
confirms that the phosphorous atoms are not coordi-
nated to the tin atom, and that the tin is in a tetrahe-
dral [SnC2S2] environment.
796(1)
494(2)
159(2)
125(2)
431(1)
672(1)
840(2)
459(2)
−64(4)
456(4)
The 31P-NMR spectrum of [Ph2Sn{2-(Ph2P)C6H4S}2]
again shows a signal at −15.3 ppm, which is practi-
cally the same value as the chemical shift in the free
ligand (−14.6 ppm) showing that the phosphorus atom
is not coordinated to the metal. The X-ray structure of
the compound in the solid state confirms this conclu-
sion. The 119Sn spectrum shows a signal at l −60 ppm,
a value in the range for four-coordinate tin compounds.
1824(4)
2669(3)
3282(3)
3002(4)
3023(5)
3304(4)
3598(4)
3571(4)
−86(2)
−254(2)
123(1)

P. Pe´rez-Lourido et al. / Journal of Organometallic Chemistry 595 (2000) 59–65
63
Fig. 1. Molecular structure of [Ph2Sn{2-(Ph2P)C6H4S}2] (2).
Table 4
It is worth nothing, that in the case of [Me2Sn{2-
,
Selected bond distances (A) and angles (°) for [Ph2Sn{2-
(Ph2P)C6H4S}2] (2)
(Ph2P)C6H4S}2] and [Ph2Sn{2-(Ph2P)C6H4S}2] the phos-
phorus signal is accompanied by satellites due to
31P–119Sn long-distance coupling.
Bond distances
The 1H-NMR spectrum of [Me2Sn{2-(Ph2PO)-6-
(Me3Si)C6H3S}2] shows two singlet signals integrating
to nine protons at high field at l 0.5 and 0.4 ppm due
to two different trimethylsilyl groups. This inequiva-
Sn(1)ꢀC(1)
Sn(1)ꢀS(1)
P(1)ꢀC(14)
P(1)ꢀC(25)
P(2)ꢀC(37)
2.133(4)
2.4941(13)
1.826(5)
1.841(4)
1.838(5)
Sn(1)ꢀC(7)
Sn(1)ꢀS(2)
P(1)ꢀC(19)
P(2)ꢀC(32)
P(2)ꢀC(43)
2.142(5)
2.5034(12)
1.821(5)
1.835(5)
1.845(4)
lence is confirmed by the presence of two signals at 0.01
Bond angles
13
and −0.01 ppm in the
C-NMR spectrum. These
C(1)ꢀSn(1)ꢀC(7) 126.7(2)
C(7)ꢀSn(1)ꢀS(1) 119.04(14)
C(7)ꢀSn(1)ꢀS(2) 102.87(14)
C(1)ꢀSn(1)ꢀS(1)
C(1)ꢀSn(1)ꢀS(2)
S(1)ꢀSn(1)ꢀS(2)
106.08(13)
109.05(12)
83.74(4)
observations suggest the presence of two bidentate lig-
ands in the complex. The 31P-NMR spectrum shows
two signals at l 38.79 and 35.14 ppm, again demon-
strating the presence of two inequivalent ligands. The
119Sn-NMR spectrum shows a signal at l −93.31 ppm,
which is in the range for six-coordinate tin compounds.
Taken as a whole, the above results show that in
[Me2Sn{2-(Ph2PO)-6-(Me3Si)C6H3S}2] the tin atom is in
an octahedral [SnC2O2S2] environment. This structure
contrasts the tetrahedral environment around the metal
in [Me2Sn{2-(Ph2P)C6H4S}2], an observation which can
be rationalized as the result of minimized steric conges-
tion resulting from the insertion of the oxygen atom
donor between the tin and the phosphorous so as to
remove the organic substituents from the vicinity of the
metal. These conclusions are supported by the X-ray
diffraction structure in the solid state.
The 1H-NMR spectrum of [Ph2Sn{2-(Ph2PO)-6-
(Me3Si)C6H3S}2] again shows two singlets at l 0.4 and
0.3 ppm due to the hydrogen atoms of two non-equiva-
lent silyl groups. The 13C-NMR spectrum shows the
signals of these groups at l 0.09 and −0.01 ppm. As in
the case of [Me2Sn{2-(Ph2PO)-6-(Me3Si)C6H3S}2], the
31P-NMR spectrum shows two signals at l 41.52 and
Fig. 2. Molecular structure of [Me2Sn{2-(Ph2PO)-6-(Me3Si)C6H3S}2]
(3).

64
P. Pe´rez-Lourido et al. / Journal of Organometallic Chemistry 595 (2000) 59–65
Table 5
splitting is too low for a six-coordinate trans tin
compound.
,
Selected bond distances (A) and angles (°) for [Me2Sn{2-(Ph2PO)-6-
(Me3Si)C6H3S}2] (3)
3.6. Mass spectra
Bond distances
Sn(1)ꢀC(1)
Sn(1)ꢀO(1)
Sn(1)ꢀS(1)
P(2)ꢀO(2)
2.117(3)
2.441(2)
2.5513(8)
1.502(2)
Sn(1)ꢀC(2)
Sn(1)ꢀO(2)
Sn(1)ꢀS(1)
P(1)ꢀO(1)
2.118(3)
2.475(2)
2.5627(8)
1.504(2)
The tin complexes were also characterized by mass
spectroscopy using the technical FAB (m/z) of the
positive ion in 2-nitrobenzyl alcohol (NBA) as base. In
all cases the molecular peak, [M]+, for each compound
is observed, as well as other peaks corresponding to
fragments of the parent peak from the loss of different
groups of the compound.
In the spectrum of the compound [Me2Sn{2-
(Ph2P)C6H4S}2] the molecular ion peak is observed at
m/z 735, as well as a peak at m/z 442, corresponding to
the [Me2Sn{2-(Ph2P)C6H4S}]+ ion. In the spectrum of
[Ph2Sn{2-(Ph2P)C6H4S}2] the molecular ion m/z 859 is
also observed, as well as a peak at m/z 567, correspond-
ing peak to the [Ph2Sn{2-(Ph2P)C6H4S}]+ ion, and also
a peak assigned to the ligand at m/z 293.
Bond angles
C(1)ꢀSn(1)ꢀC(2) 152.8(2)
C(2)ꢀSn(1)ꢀO(1)
C(2)ꢀSn(1)ꢀO(2)
C(1)ꢀSn(1)ꢀS(1) 101.65(10)
O(1)ꢀSn(1)ꢀS(1)
C(1)ꢀSn(1)ꢀS(2)
O(1)ꢀSn(1)ꢀS(2) 172.89(6)
S(1)ꢀSn(1)ꢀS(2) 91.56(3)
C(1)ꢀSn(1)ꢀO(1)
C(1)ꢀSn(1)ꢀO(2)
O(1)ꢀSn(1)ꢀO(2) 104.49(8)
C(2)ꢀSn(1)ꢀS(1) 97.90(11)
O(2)ꢀSn(1)ꢀS(1) 173.90(5)
C(2)ꢀSn(1)ꢀS(2) 100.95(11)
O(2)ꢀSn(1)ꢀS(2)
82.30(12)
79.82(11)
82.00(12)
82.76(12)
81.60(6)
97.30(10)
82.36(5)
35.21 ppm. On the other hand, the 119Sn-NMR spec-
trum shows a signal at l −260 ppm. This value is
compatible with the presence of a six-coordinate tin
atom. Consequently, it is proposed that in [Ph2Sn{2-
(Ph2PO)-6-(Me3Si)C6H3S}2] the tin atom is in an octa-
hedral [SnC2O2S2] environment.
For
[Me2Sn{2-(Ph2PO)-6-(Me3Si)C6H3S}2],
the
molecular ion peak is observed at m/z 911, as well as
peaks at m/z 531 and m/z 383 corresponding to the
[Me2Sn{2-(Ph2P)-6-(Me3Si)C6H3S}]+ ion and proto-
nated ligand, respectively. For the [Ph2Sn{2-(Ph2PO)-6-
(Me3Si)C6H3S}2] complex, the molecular ion at m/z
1035 is observed, as well as the peak corresponding to
the [Me2Sn{2-(Ph2PO)6-(Me3Si)C6H3S}]+ ion at m/z
655.
3.5. Mo¨ssbauer spectra
The Mo¨ssbauer parameters for these compounds are
collected in Table 6. The quadrupole splitting data
for [Me2Sn{2-(Ph2P)C6H4S}2] and [Ph2Sn{2-(Ph2P)-
C6H4S}2] are compatible with a tetrahedral arrange-
ment around the metal, although the value for
[Ph2Sn{2-(Ph2P)C6H4S}2] seems to be somewhat high
and at the limit of the normally accepted interval for a
tetrahedral compound, this geometry having been
confirmed by X-ray diffraction. The parameters for
[Me2Sn{2(Ph2PO)-6-(Me3Si)C6H3S}2] are reasonable
for the distorted octahedral structure found by X-ray
diffraction.
4. Supplementary material
Crystallographic data for the structural analyses
have been deposited at the Cambridge Crystallo-
graphic data Centre, CCDC nos. 127416 for com-
pound 2 and 127300 for compound 3. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge, CB2
1EZ, UK (Fax: +44-1223-336033; e-mail: de-
posit@ccdc.cam.ac.uk or www: http://www.ccdc.
cam.ac.uk).
The isomer shift of the compound [Ph2Sn{2-
(Ph2PO)6-(Me3Si)C6H3S}2] is compatible with a trans
octahedral structure, but the value of the quadrupole
Table 6
Mo¨ssbauer parameters for the complexes a
b
Compound
l
(mm s−1
)
DEQ (mm s−1
)
Y (mm s−1
)
Y2/1
[Me2Sn{2-(Ph2P)C6H4S}2]
[Ph2Sn{2-(Ph2P)C6H4S}2]
[Me2Sn{2-(Ph2PO)-6-(Me3Si)C6H3S}2]
[Ph2Sn{2-(Ph2PO)-6-(Me3Si)C6H3S}2]
1.54
1.46
1.54
1.43
2.35
3.21
2.99
2.60
0.80
0.75
0.83
0.81
1.11
0.96
1.14
0.98
a Spectra were recorded at 80 K.
b Relative to SnO2 at room temperature.

P. Pe´rez-Lourido et al. / Journal of Organometallic Chemistry 595 (2000) 59–65
65
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[7] D.C. Creagh, J.W. McAuley, International Tables for X-ray
Crystallography, vol. C, Table 4, Kluwer Academic, Boston,
1992.
[8] SHELXTL PCTM Siemens Analytical X-ray Instruments, Inc.,
Madison, WI, 1990.
Acknowledgements
We thank the Xunta de Galicia (Xuga 20910B93) for
financial support.
[9] (a) G.M. Sheldrick, Acta Crystallogr. Sect. A 46 (1990) 467. (b)
G.M. Sheldrick, SHELX-97, Program for Crystal Structure Refin-
ement, University of Go¨ttingen, 1997.
[10] E.J. Huhey, E.A. Keiter, R.L. Keiter, Inorganic Chemistry,
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