Synthesis and characterization of aluminum-containing tin(IV) heterobimetallic sulfides

Article abstract of DOI:10.1021/ic052139m

Three novel aluminum-containing tin(IV) heterobimetallic sulfides are reported. The reaction of [LAl(SLi)₂(THF)₂]₂ (1) [L = HC(CMeNAr)₂, Ar = 2,6-iPr₂C₆H ₃] with Ph₂Sn

Full text of DOI:10.1021/ic052139m

Inorg. Chem. 2006, 45, 3312−3315
Synthesis and Characterization of Aluminum-Containing Tin(IV)
Heterobimetallic Sulfides
Zhi Yang,† Xiaoli Ma,† Vojtech Jancik,‡ Zhensheng Zhang,† Herbert W. Roesky,*,† Jorg Magull,†
1
Mathias Noltemeyer,† Hans-Georg Schmidt,† Raymundo Cea-Olivares,‡ and Rube´n A. Toscano‡
Institut fu¨r Anorganische Chemie der Georg-August-UniVersita¨t Go¨ttingen, Tammannstrasse 4,
D-37077 Go¨ttingen, Germany, and Instituto de Qu´ımica, UNAM, Circuito Exterior Cd.
UniVersitaria, Mexico D. F. 04510
Received December 14, 2005
Three novel aluminum-containing tin(IV) heterobimetallic sulfides are reported. The reaction of [LAl(SLi)2(THF)2]2
(1) [L HC(CMeNAr)2, Ar 2,6-iPr2C6H3] with Ph2SnCl2, Me2SnCl2, and SnCl4 in THF respectively afforded
LAl( -S)2SnPh2 (2), LAl( -S)2SnMe2 (3), and LAl( -S)2Sn( -S)2AlL (4) in moderate yields. Compounds 2, 3, and
)
)
µ
µ
µ
µ
4 were characterized by elemental analysis, NMR, electron-impact mass spectrometry, and single-crystal X-ray
structural analysis.
Introduction
limited. Moreover, aluminum-containing heterobimetallic
sulfides have not been reported very often. There are only a
few examples known containing the Al-(µ-S)-Fe3 and
Al-(µ-S)-M (M ) Zr and Ti) moieties.4,5 Recently,
[LAl(SLi)2(THF)2]2 (1) was prepared, and this is a valuable
precursor for the preparation of heterobimetallic sulfides.4
The first aluminum-containing heterotrimetallic sulfide of
composition L2Al2Ge4Li2S7 has been prepared by reacting 1
with GeCl2‚dioxane.6 Herein, we report on the reaction of 1
with organotin dichlorides and tin tetrachloride to yield LAl-
(µ-S)2SnR2 (R ) Me and Ph) and the spirocyclic heterotri-
metallic sulfide LAl(µ-S)2Sn(µ-S)2AlL.
Organometallic chalcogen compounds have attracted much
interest because of their application as catalysts in industry.
More recently, attention has been paid to heterobimetallic
chalcogen compounds not only from the viewpoint of
fundamental chemistry but also because of their catalytic
properties.1 Aluminum is the most abundant metal in the
earth’s crust; therefore, many aluminum-containing hetero-
bimetallic oxides have been synthesized and characterized.2
Organometallic sulfides are less stable than the corresponding
oxides, and synthetic methods for their preparation are
* Author to whom correspondence should be addressed. Fax: (+49) 551-
39-3373. E-mail: hroesky@gwdg.de.
Experimental Section
† Institut fu¨r Anorganische Chemie der Georg-August-Universita¨t Go¨t-
tingen.
General Procedures. All manipulations were carried out under
a purified nitrogen atmosphere using Schlenk techniques or inside
a Mbraun MB 150-GI glovebox. All solvents were distilled from
Na/benzophenone ketyl prior to use. Commercially available
chemicals were purchased from Aldrich or Fluka and used as
received. SnCl4‚2THF (THF ) tetrahydrofuran) was prepared
according to a literature procedure.7 Elemental analyses were
performed by the Analytisches Labor des Instituts fu¨r Anorganische
‡ Instituto de Qu´ımica, UNAM.
(1) (a) Takeda, N.; Tokitoh, N.; Okazaki, R. Top. Curr. Chem. 2003, 231,
153-202. (b) DuBois, M. R. Chem. ReV. 1989, 89, 1-9. (c) Cope´ret,
C.; Chabanas, M.; Saint-Arroman, R. P.; Basset, J.-M. Angew Chem.
2003, 115, 164-191; Angew. Chem., Int. Ed. 2003, 42, 156-181. (d)
Sinonnet-Je´gat, C.; Se´cheresse, F. Chem. ReV. 2001, 101, 2601-2611.
(e) Draganjac, M.; Rauchfuss, T. B. Angew. Chem. 1985, 97, 745-
760; Angew. Chem., Int. Ed. Engl. 1985, 24, 742-757. (f) Mu¨ller,
A.; Jaegermann, W.; Enemark, J. H. Coord. Chem. ReV. 1982, 46,
245-280. (g) Mu¨ller, A.; Diemann, E.; Jostes, R.; Bo¨gge, H. Angew.
Chem. 1981, 93, 957-977; Angew. Chem., Int. Ed. Engl. 1981, 20,
934-954. (h) Coucouvanis, D. AdV. Inorg. Chem. 1998, 45, 1-73.
(i) Kolis, J. W. Coord. Chem. ReV. 1990, 105, 195-219. (j) Mu¨ller,
A. Polyhedron 1986, 5, 323-340. (k) Okazaki, R. Phosphorus, Sulfur
Silicon Relat. Elem. 2001, 168, 41-50.
(2) See, for example: (a) Chai, J.; Jancik, V.; Singh, S.; Zhu, H.; He, C.;
Roesky, H. W.; Schmidt, H.-G.; Noltemeyer, M.; Hosmane, N. S. J.
Am. Chem. Soc. 2005, 127, 7521-7528. (b) Bai, G.; Singh, S.; Roesky,
H. W.; Noltemeyer, M.; Schmidt, H.-G. J. Am. Chem. Soc. 2005, 127,
3449-3455. (c) Sharma, N. B.; Singh, A.; Mehrotra, R. C. J.
Organomet. Chem. 2005, 690, 96-102.
Chemie der Universita¨t Go¨ttingen. H, 13C, 27Al, and 119Sn NMR
1
(3) Weers, J. J.; Eyman, D. P. J. Organomet. Chem. 1985, 286, 47-54.
(4) Jancik, V.; Roesky, H. W.; Neculai, D.; Neculai, A. M.; Herbst-Irmer,
R. Angew. Chem. 2004, 116, 6318-6322; Angew. Chem., Int. Ed.
2004, 43, 6192-6196.
(5) Harlan, C. J.; Barron, A. R. J. Cluster Sci. 1996, 7, 455-467.
(6) Yang, Z.; Ma, X.; Oswald, R. B.; Roesky, H. W.; Cui, C. M.; Schmidt,
H.-G.; Noltemeyer, M. Angew. Chem., Int. Ed. in press.
(7) Willey, G. R.; Woodman, T. J.; Deeth, R. J.; Errington W. Main Group
Met. Chem. 1998, 21, 583-591.
3312 Inorganic Chemistry, Vol. 45, No. 8, 2006
10.1021/ic052139m CCC: $33.50
© 2006 American Chemical Society
Published on Web 03/18/2006

Aluminum-Containing Tin(IV) Heterobimetallic Sulfides
Table 1. Crystallographic Data for Compound 2, 3, 3a, and 4
2‚toluene
3
3‚toluene (3a)
4‚1.5C7H8‚1THF
formula
fw
C48H59AlN2S2Sn
873.76
C31H47AlN2S2Sn
657.50
C38H55AlN2S2Sn
749.64
C72.5H102Al2N4OS4Sn
1346.47
temp (K)
cryst syst
space group
a (Å)
b (Å)
c (Å)
133(2)
monoclinic
P21/c
9.543(1)
23.398(1)
20.409(1)
90
95.74(1)
90
4534(1)
4
1.280
0.709
294(2)
monoclinic
P21/c
10.502(2)
26.736(4)
12.615(3)
90
104.74(3)
90
3426(1)
4
1.275
0.914
133(2)
triclinic
P1h
8.808(2)
13.280(3)
17.283(4)
79.57(3)
75.42(3)
87.69(3)
2061(1)
133(2)
monoclinic
P21/c
12.342(1)
18.604(1)
30.762(1)
90
92.44(1)
90
7057(1)
4
R (deg)
â (deg)
γ (deg)
V (Å3)
Z
2
Fc (Mg/m3)
1.294
0.823
784
1.267
0.550
2852
M (mm-1
F(000)
)
1824
1368
Θ range (deg)
1.74-24.84
-11 e h e 9
-27 e k e 27
-24 e l e 24
64304
7812 (0.0546)
7812/0/486
0.988
1.83-25.03
-12 e h e 12
-31 e k e 31
-15 e l e 15
27934
6042 (0.0438)
6042/0/349
1.037
1.56-24.84
-10 e h e 10
-15 e k e 15
-20 e l e 20
34091
6640 (0.0576)
6640/0/410
1.017
1.65-24.83
-14 e h e 14
-21 e k e 21
-36 e l e 36
103650
12130 (0.0838)
12130/1279/767
1.014
index ranges
no. of reflns collected
no. of independent R(int)
no. of data/restraints/params
GOF/F2
R1a, wR2b[I > 2σ(I)]
R1a, wR2b(all data)
0.0312, 0.0760
0.0443, 0.0795
0.0446, 0.1034
0.0586, 0.1106
0.0274, 0.0677
0.0352, 0.0700
0.0780, 0.2297
0.1115, 0.2509
spectra were recorded on Bruker AM 300 and 500 spectrometers
and IR spectra on a Bio-Rad Digilab FTS-7 spectrometer. Electron-
impact mass spectra (EI-MS) were measured on a Finnigan MAT
8230 or a Varian MAT CH5 instrument. Melting points were
measured in sealed glass tubes and were not corrected.
25 °C, AlCl3‚6H2O): δ (ppm) 114. 119Sn NMR (186.49 MHz,
CDCl3, 25 °C, SnMe4): δ (ppm) 133. Anal. Calcd for C31H47-
AlN2S2Sn (657.52): C, 56.63; H, 7.20; N, 4.26. Found: C, 56.24;
H, 7.56; N 3.96%.
Preparation of LAl(µ-S)2Sn(µ-S)2AlL (4). SnCl4 (0.26 g, 0.12
mL, 1 mmol) was added dropwise to a solution of 1 (1.33 g, 1
mmol) in THF (20 mL) at -30 °C. After the addition was complete,
the reaction mixture was allowed to warm to room temperature.
The solvent was removed in vacuo. The solid was extracted with
toluene (10 mL) and kept at room temperature for 2 days to afford
colorless crystals. Yield: 0.97 g (85%).
Preparation of LAl(µ-S)2SnPh2 (2). A solution of Ph2SnCl2
(0.69 g, 2 mmol) in THF (10 mL) was added dropwise to a solution
of 1 (1.33 g, 1 mmol) in THF (20 mL) at -30 °C. After the addition
was complete, the reaction mixture was allowed to warm to room
temperature. The solvent was removed in vacuo. The solid was
extracted with toluene (10 mL), and the extract was kept at room
temperature for 2 days to afford 2 as colorless crystals. Yield: 1.42
g (91%). mp: 251 °C. EI-MS m/z (%): 782 (40) [M+], 705 (100)
Alternative Preparation of LAl(µ-S)2Sn(µ-S)2AlL (4). 1 (1.33
g, 1 mmol) and SnCl4‚2THF (0.41 g, 1 mmol) were mixed as solids
in a flask. The flask was placed in liquid nitrogen, and toluene (50
mL) was added slowly. The reaction mixture was allowed to warm
to ambient temperature and was stirred overnight. The resulting
suspension was filtered, and all volatiles from the filtrate were
removed in vacuum to leave a residue that was washed with hex-
ane to give 1.1 g of microcrystalline 4. Yield: 97%. mp: 321 °C.
1
[M+ - Ph], 627 (30) [M+ - 2Ph]. H NMR (300.13 MHz, C6D6,
25 °C, TMS): δ (ppm) 7.23-7.16 (m, 6 H, Ar-H), 7.10-7.02 (m,
10 H, Ph-Sn), 4.90 (s, 1 H, γ-H), 3.55 (sept, 3JH-H ) 6.8 Hz, 4 H,
CHMe2), 1.60 (s, 6 H, Me), 1.49 (d, 3JH-H ) 6.8 Hz, 12 H, CHMe2),
3
1.12 (d, JH-H ) 6.8 Hz, 12 H, CHMe2). 13C NMR (75.48 MHz,
C6D6, 25 °C, TMS): δ (ppm) 170.9 (CN), 145.1, 141.3, 139.5,
136.0, 129.3, 125.6, 124.9 (Ar and Sn-Ph), 98.1 (γ-C), 29.2
(CHMe2), 25.4 (CHMe2), 23.9 (CHMe2), 21.4 (Me). 27Al NMR
(78.21 MHz, C6D6, 25 °C, AlCl3‚6H2O): δ (ppm) 114.5. 119Sn
NMR (186.49 MHz, C6H6, 25 °C, SnMe4): δ (ppm) -38. Anal.
Calcd for C41H51AlN2S2Sn‚1/4C7H8 (804.66): C, 63.88; H, 6.59;
N, 3.48. Found: C, 63.92; H, 6.70; N, 3.35%.
1
EI-MS m/z (%): 1136.4 (12) [M+], 403 (100) [L-Me]. H NMR
(300.13 MHz, C6D6, 25 °C, TMS): δ (ppm) 7.17-7.05 (m, 12 H,
Ar-H), 4.73 (s, 2 H, γ-H), 3.35 (sept, 3JH-H ) 6.8 Hz, 8 H, CHMe2),
3
1.46 (s, 12 H, Me), 1.44 (d, JH-H ) 6.8 Hz, 24 H, CHMe2), 1.05
(d, 3JH-H ) 6.8 Hz, 24 H, CHMe2). 13C NMR (75.48 MHz, C6D6,
25 °C, TMS): δ (ppm) 171.0 (CN), 144.5, 138.9, 129.3, 124.7
(p-, m-, o-, i-C of Ar), 98.4 (γ-C), 29.0 (CHMe2), 25.9 (CHMe2),
23.8 (CHMe2), 21.4 (Me). 27Al NMR (78.21 MHz, C6D6, 25 °C,
AlCl3‚6H2O): δ (ppm) 114. 119Sn NMR (186.49 MHz, C6H6, 25
°C, SnMe4): δ (ppm) 5.0. Anal. Calcd for C58H82Al2N4S4Sn
(1136.40): C, 61.31; H, 7.27; N, 4.93. Found: C, 60.96; H, 6.98;
N, 4.50.
Preparation of LAl(µ-S)2SnMe2 (3). The preparation of 3 is
like that of 2 except from Me2SnCl2 (0.44 g, 2 mmol) and 1 (1.33
g, 1 mmol). Product 3 was isolated as colorless crystals. Yield:
1.184 g (90%). mp: 214-215 °C. EI-MS m/z (%): 658 (20) [M+],
1
643 (100) [M+ - Me], 627 (5) [M+ - 2Me]. H NMR (300.13
MHz, CDCl3, 25 °C, TMS): δ (ppm) 7.25-7.17 (m, 6 H, Ar-H),
5.25 (s, 1 H, γ-H), 3.32 (sept, 3JH-H ) 6.8 Hz, 4 H, CHMe2), 1.84
Single-Crystal X-ray Structure Determination and Refine-
ment. The crystallographic data for compounds 2‚toluene, 3‚
toluene, and 4‚1.5toluene‚THF were collected on a Stoe IPDS II
array detector system, whereas the data collection for compound 3
was performed on a Bruker three-circle diffractometer equipped
with an Apex CCD area detector. Graphite-monochromated Mo
KR radiation (λ ) 0.710 73 Å) was used in all four experiments.
3
(s, 6 H, Me), 1.36 (d, JH-H ) 6.8 Hz, 12 H, CHMe2), 1.12 (d,
3JH-H ) 6.8 Hz, 12 H, CHMe2), 0.40 (s, 6 H, 2J(117)Sn-H ) 1.4 Hz,
2J(119)Sn-H ) 1.4 Hz, Me-Sn). 13C NMR (75.48 MHz, CDCl3, 25
°C, TMS): δ (ppm) 170.7 (CN), 144.7, 138.9, 127.0, 124.1 (p-,
m-, o-, i-C of Ar), 98.0 (γ-C), 28.9 (CHMe2), 26.0 (CHMe2), 23.6
(CHMe2), 21.5 (Me), 2.6 (Sn-Me). 27Al NMR (78.21 MHz, CDCl3,
Inorganic Chemistry, Vol. 45, No. 8, 2006 3313

Yang et al.
Scheme 1. Preparation of Compounds 2 and 3
Scheme 2. Preparation of Compound 4
The structures were solved by direct methods (SHELXS-90)8
and refined against F2 using SHELXL-97.9 In the case of 4, the
molecule is well-defined, but global anisotropic displacement
parameter restraints were used to identify spurious solvents near
crystallographic axes. Toluene was treated as a rigid body, and
THF was refined using SAME/SADI restraints. Hydrogen atoms
were included in geometrically idealized positions and refined
isotropically using the riding model with Uiso tied to the Uiso of the
parent atoms. A summary of cell parameters, data collection,
structure solution, and refinement for all structures is given in
Table 1.
Figure 1. Molecular structure of 2. Thermal ellipsoids are drawn at the
50% level. The solvent molecule and hydrogen atoms are omitted for clarity.
Results and Discussion
Compounds 2 and 3 were prepared by adding dropwise,
in THF, Ph2SnCl2 or Me2SnCl2, respectively, to 1 in THF at
low temperature (Schemes 1 and 2). Because SnCl4 is a
liquid, it was added directly to the THF solution of 1.
Compound 1 is sparingly soluble in THF, and therefore, it
formed a suspension in THF at low temperature. However,
after adding Ph2SnCl2, Me2SnCl2, or SnCl4, the suspension
became clear and the light yellow color turned very quickly
to colorless. This is an indication for the progress of the
reaction. Alternatively, compound 4 can be prepared by the
direct reaction of 1 and SnCl4‚2THF in toluene to avoid the
decomposition of 1 by traces of free HCl present in SnCl4.
Compounds 2, 3, and 4 are all colorless solids and are well-
soluble in toluene, benzene, and so forth. They were
characterized by EI-MS spectra; elemental analysis; 1H, 13C,
27Al, and 119Sn NMR investigations; and single-crystal X-ray
diffraction studies. The 1H NMR spectra of 2, 3, and 4 exhibit
one set of resonances for the ligand (L). Compound 2 shows
the Sn-Ph resonances in the range from δ 7.10 to 7.02 ppm,
which are distinct from those of the Ar-H resonances (δ
7.23-7.16 ppm). Compound 3 exhibits a Sn-Me at δ 0.40
ppm in a 6:1 ratio to that of the γ-H proton. Compound 4
displays only one set of resonances for the ligand (L), indi-
cating that the two ligands are in the same chemical
environment. The 27Al NMR spectra of 2-4 show the
resonances in a narrow range (113-114 ppm), and these are
Figure 2. Molecular structure of 3. Thermal ellipsoids are drawn at the
50% level. The solvent molecule and hydrogen atoms are omitted for clarity.
comparable to those of compounds with four-coordinate
aluminum.10 The electron impact mass spectra of 2, 3, and
4 (m/z ) 782, 658, and 1136) show the parent ion [M+] with
its isotopic pattern. Particularly interesting is the ion of
composition [LAl(µ-S)2Sn] (m/z ) 627), which appears in
the fragmentation of both 2 and 3.
The compositions of 2, 3, and 4 were assigned by X-ray
structural analysis. Colorless crystals of 2‚toluene, 3‚toluene,
and 4‚1.5toluene‚THF were obtained from toluene at -28
°C, whereas the solvent-free form of 3 was obtained by
its crystallization from hexane at -32 °C. The structure
of 4‚1.5toluene‚THF contains disordered solvent mole-
cules, which could be refined using restraints and rigid body
constraints. Some data collection and refinement details are
(10) See, for example: (a) Peng, Y.; Fan, H. J.; Zhu, H. P.; Roesky, H.
W.; Magull, J.; Hughes, C. E. Angew. Chem. 2004, 116, 3525-3527;
Angew. Chem., Int. Ed. 2004, 43, 3443-3445. (b) Yang, Z.; Ma, X.;
Oswald, R. B.; Roesky, H. W.; Zhu, H. P.; Schulzke, C.; Starke, K.;
Baldus, M.; Schmidt, H.-G.; Noltemeyer, M. Angew. Chem. 2005, 117,
7234-7236; Angew. Chem., Int. Ed. 2005, 44, 7072-7074. (c) Qian,
B.; Ward, D. L.; Smith, M. R., III. Organometallics 1998, 17, 3070-
3076.
(8) Sheldrick, G. M. Acta Crystallogr., Sect. A 1990, 46, 467-473.
(9) Sheldrick, G. M. SHELXL-97; University of Go¨ttingen: Go¨ttingen,
Germany, 1997.
3314 Inorganic Chemistry, Vol. 45, No. 8, 2006

Aluminum-Containing Tin(IV) Heterobimetallic Sulfides
Table 4. Selected Bond Distances (Å) and Angles (deg) for
Compound 4
Al(1)-N(1)
1.875(6)
1.882(6)
2.239(3)
2.230(3)
2.397(2)
2.388(2)
3.037(2)
102.2(1)
81.8(1)
82.1(1)
Al(1)-N(2)
1.884(6)
1.882(6)
2.239(3)
2.253(3)
2.378(2)
2.392(2)
3.035(2)
102.0(1)
82.2(1)
81.6(1)
Al(2)-N(3)
Al(2)-N(4)
Al(1)-S(1)
Al(1)-S(2)
Al(2)-S(3)
Al(2)-S(4)
Sn(1)-S(1)
Sn(1)-S(2)
Sn(1)-S(3)
Sn(1)-S(4)
Sn(1)-Al(1)
Sn(1)-Al(2)
S(1)-Al(1)-S(2)
Al(1)-S(1)-Sn(1)
Al(2)-S(3)-Sn(1)
S(1)-Sn(1)-S(2)
S(1)-Sn(1)-S(4)
S(1)-Sn(1)-S(3)
Al(1)-Sn(1)-Al(2)
S(3)-Al(2)-S(4)
Al(1)-S(2)-Sn(1)
Al(2)-S(4)-Sn(1)
S(3)-Sn(1)-S(4)
S(2)-Sn(1)-S(3)
S(2)-Sn(1)-S(4)
93.7(1)
93.6(1)
119.4(1)
114.8(1)
122.0(1)
115.6(1)
173.3(1)
acid. In the structures of compounds 2, 3, and 3a (Figures 1
and 2), the AlS2Sn four-membered rings are both perpen-
dicular to the AlN2C3 plane of the ligand (L) as well as to
the C-Sn-C planes. Consequently, the ligand plane and
the C-N-C plane are parallel in 2, 3, and 3a. In the struc-
ture of compound 4 (Figure 3), there are four conjoint
planes: consisting of two six-membered ligand (L) planes
and two four-membered AlS2Sn planes, where every inter-
facing plane is perpendicular to its neighbors. The Sn-S
bonds in 2 [2.402(1) and 2.403(1) Å] are slightly longer than
those in 4 (2.378-2.397 Å), similar to those in 3 [2.395(1)
and 2.413(1) Å], but shorter than those in 3a [2.410(1) and
2.414(1) Å]. They are in the range of those reported
previously (2.329-2.574 Å).11 The Al-S-Sn angles of 2,
3, 3a, and 4 are very similar: 2 (81.4° and 81.5°), 3 (81.7°
and 82.4°), 3a (82.5° and 82.5°), and 4 (81.8°, 82.2°, 82.1°,
and 81.6°) (see Tables 2-4).
Figure 3. Molecular structure of 4. Thermal ellipsoids are drawn at
the 50% level. The solvent molecule and hydrogen atoms are omitted for
clarity.
Table 2. Selected Bond Distances (Å) and Angles (deg) for
Compound 2
Al(1)-N(1)
1.882(2)
2.233(1)
2.403(1)
3.026(1)
81.4(1)
Al(1)-N(2)
1.889(2)
2.229(1)
2.402(1)
103.3(1)
81.5(1)
Al(1)-S(1)
Al(1)-S(2)
Sn(1)-S(1)
Al(1)-Sn(1)
Al(1)-S(1)-Sn(1)
S(2)-Sn(1)-S(1)
Sn(1)-S(2)
S(1)-Al(1)-S(2)
Al(1)-S(2)-Sn(1)
C(31)-Sn(1)-C(41)
93.5(1)
117.0(1)
Table 3. Selected Bond Distances (Å) and Angles (deg) for
Compounds 3 and 3a
Compound 3
Al(1)-N(1)
1.902(3)
2.227(1)
2.413(1)
3.037(1)
81.7(1)
Al(1)-N(2)
1.893(3)
2.213(1)
2.395(1)
102.9(1)
82.4(1)
Al(1)-S(1)
Al(1)-S(2)
Sn(1)-S(1)
Al(1)-Sn(1)
Al(1)-S(1)-Sn(1)
S(2)-Sn(1)-S(1)
Sn(1)-S(2)
Conclusion
S(2)-Al(1)-S(1)
Al(1)-S(2)-Sn(1)
C(30)-Sn(1)-C(31)
In summary, we have synthesized and characterized a new
class of aluminum-sulfur derivatives from compound 1 and
various tin chlorides.
92.5(3)
111.8(2)
Compound 3a
Al(1)-N(1)
1.906(2)
2.234(1)
2.410(1)
3.063(1)
82.5(1)
Al(1)-N(2)
1.882(2)
2.225(1)
2.414(1)
101.9(1)
82.5(1)
Al(1)-S(1)
Al(1)-S(2)
Sn(1)-S(1)
Al(1)-Sn(1)
Al(1)-S(1)-Sn(1)
S(1)-Sn(1)-S(2)
Sn(1)-S(2)
Acknowledgment. We are grateful for financial support
from the Fonds der Chemischen Industrie and the Go¨ttinger
Akademie der Wissenschaften. V.J. thanks UNAM for his
postdoctoral fellowship.
S(1)-Al(1)-S(2)
Al(1)-S(2)-Sn(1)
C(30)-Sn(1)-C(31)
91.8(1)
112.1(2)
given in Table 1. Further details are in the Supporting
Information.
Supporting Information Available: CIF files for compounds
2, 3, 3a, and 4. This material is available free of charge via the
Internet at http://pubs.acs.org.
Compound 3‚toluene crystallizes in the triclinic space
group P1h, while 2‚toluene, 3, and 4‚1.5toluene‚THF crystal-
lize in the monoclinic space group P21/c. The toluene
solvated form of 3 will be, for clarity, noted as 3a in the
following text. The characteristics of 2, 3, and 3a are the
(µ-S)2 bridges between the aluminum and tin atoms generat-
ing novel heterobimetallic sulfides. Compound 4 displays a
spirocyclic arrangement with the tin atom at the center of
the Al-(µ-S)2-Sn-(µ-S)2-Al moiety and represents the
first example of a lipophilic complex of ortho-thiostannous
IC052139M
(11) See, for example: (a) Sekiguchi, A.; Izumi, R.; Lee, V. Y.; Ichinohe,
M. Organometallics 2003, 22, 1483-1486. (b) Zimmermann, C.;
Anson, C. E.; Weigend, F.; Cle´rac, R.; Dehnen, S. Inorg. Chem. 2005,
44, 5686-5695. (c) Palchik, O.; Lyer, R. G.; Liao, J. H.; Kanatzidis,
M. G. Inorg. Chem. 2003, 42, 5052-5054. (d) Borisova, I. V.; Eaborn,
C.; Hill, M. S.; Khrustalev, V. N.; Kuznetzova, M. G.; Smith, J. D.;
Ustynyuk, Y. A.; Lunin, V. V.; Zemlyansky, N. N. Organometallics
2002, 21, 4005-4008.
Inorganic Chemistry, Vol. 45, No. 8, 2006 3315