Phosphane-catalyzed reactions of LAlH2 with elemental chalcogens; preparation of [LAl(μ-E)2AlL] [E = S, Se, Te, L = HC{C(Me)N(Ar)}2, Ar = 2,6-iPr2C6H3]

Article abstract of DOI:10.1002/ejic.200400062

Addition of catalytic amounts of a phosphane to a reaction mixture containing LAlH₂ [2; L = HC{C(Me)N(Ar)}₂, Ar = 2,6-iPr₂C₆H₃] and elemental Se or Te resulted in the formation of poorly soluble [LAl(μ-Se)₂AlL] (3) and [LAl(μ-Te)₂AlL] (4), respectively. The sulfur analogue [LAl(μ-S)₂AlL] (5) could not be obtained from the direct reaction of 2 with elemental sulfur; consequently, its synthesis was successfully achieved from the reaction of [LAlH₂] and [LAl(SH)₂]. A possible mechanism for the formation of [LAl(μ-Se)₂AlL] and [LAlμ-Te)_2-. AlL] is discussed. The molecular structures of compounds 3-5 were determined by X-ray structure analyses. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200400062

FULL PAPER
Phosphane-Catalyzed Reactions of LAlH2 with Elemental Chalcogens;
Preparation of [LAl(µ-E)2AlL] [E ؍ S, Se, Te, L ؍ HC{C(Me)N(Ar)}2,
Ar ؍ 2,6-iPr2C6H3]
Vojtech Jancik,[a] Monica M. Moya Cabrera,[b] Herbert W. Roesky,*[a]
Regine Herbst-Irmer,[a] Dante Neculai,[a] Ana M. Neculai,[a] Mathias Noltemeyer,[a] and
Hans-Georg Schmidt[a]
Dedicated to Professor Raymundo Cea Olivares
Keywords: Aluminum / Catalysis / Chalcogens / Phosphanes / Reaction mechanisms
Addition of catalytic amounts of a phosphane to a reaction
mixture containing LAlH2 [2; L = HC{C(Me)N(Ar)}2, Ar = 2,6-
iPr2C6H3] and elemental Se or Te resulted in the formation
of poorly soluble [LAl(µ-Se)2AlL] (3) and [LAl(µ-Te)2AlL] (4),
respectively. The sulfur analogue [LAl(µ-S)2AlL] (5) could not
be obtained from the direct reaction of 2 with elemental sul-
fur; consequently, its synthesis was successfully achieved
from the reaction of [LAlH2] and [LAl(SH)2]. A possible me-
chanism for the formation of [LAl(µ-Se)2AlL] and [LAl(µ-Te)2-
AlL] is discussed. The molecular structures of compounds 3−5
were determined by X-ray structure analyses.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
stituents present on the aluminum. Thus, the [AlE]n core
can be either square planar (n ϭ 2),[4Ϫ13,17] cubic (n ϭ
4)[13Ϫ17] or adopt a hexagonal drum structure (n ϭ 6).[14]
Other examples containing Al and E in a ratio that deviates
from 1:1 have also been reported to exhibit a bent
AlϪEϪAl moiety, adamantane-like Al4E6 or more complex
structures.[3,20Ϫ24] We have recently shown that [LAlH2] (2),
prepared from LH and AlH3·NMe3, reacts with elemental
selenium[3] and, in the presence of a phosphane as catalyst,
also with elemental sulfur,[2] to give species of the general
formula [LAl(EH)2] (E ϭ Se, S). The selenium derivative is
thermodynamically unstable and decomposes to yield
[{LAl(SeH)}2Se] with elimination of H2Se.[3] Nevertheless,
no product formation was observed from the reaction of
LAlH2 with elemental Te, although extreme reaction con-
ditions were used. Herein, we report on the significant in-
fluence of catalytic amounts of phosphane in the reaction
of 2 and Se and Te leading to [LAl(µ-Se)2AlL] (3) and
[LAl(µ-Te)2AlL] (4), respectively. [LAl(µ-S)2AlL] (5) could
not be obtained using this protocol, therefore 5 was synthe-
sized by the direct reaction of [LAl(SH)2] with [LAlH2].
Aluminum compounds containing heavier Group 16 ele-
ments have been comparatively less-well studied than those
containing AlϪO bonds, mainly due to the thermodynamic
stability of the latter species. Recently, we have reported the
preparation of unusual species of composition [LAl(EH)2]
[L ϭ HC{C(Me)N(Ar)}2, Ar ϭ 2,6-iPr2C6H3, E ϭ O, S,
Se],[1Ϫ3] as well as the catalytic role of P(NMe2)3 in the syn-
thesis of [LAl(SH)2] (1).[2] As an extension of our interest
in this type of compounds, we explored the influence of
phosphanes on the LAlH2/Se(Te) system. So far, there are
only a few examples of compounds containing AlϪE moiet-
ies in which the chalcogen atom is not directly bonded to
any alkyl, aryl or trialkylsilyl group.[4Ϫ25] Three different
aggregation modes have been observed for species contain-
ing Al and chalcogen atoms in a 1:1 molar ratio, mainly
depending on the hapticity of the chalcogen atom. In these
systems, the chalcogens can act either as a µ- or µ3-bridging
ligand as a consequence of the steric hindrance of the sub-
[a]
Institute of Inorganic Chemistry, University of Göttingen,
Tammannstrasse 4, 37077 Göttingen, Germany
Fax: ϩ49-551-393-373
E-mail: hroesky@gwdg.de
Results and Discussion
[b]
´
Instituto de Quımica, UNAM, Circuito Exterior Cd.
Universitaria,
Addition of catalytic amounts of P(NMe2)3 or PMe3 to
a suspension of 2 and Se or Te resulted in the formation of
[LAl(µ-E)2AlL] (3 E ϭ Se; 4 E ϭ Te) in high yields at ambi-
´
Coyoacan, D. F. 04510, Mexico
Fax: ϩ52-55-6162203 or -6162217
E-mail: monica.moya@correo.unam.mx
3508
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejic.200400062
Eur. J. Inorg. Chem. 2004, 3508Ϫ3512

Phosphane-Catalyzed Reactions of LAlH2 with Elemental Chalcogens
FULL PAPER
ent temperature. Compounds 3 and 4 are sparingly soluble to isolate such intermediates. Scheme 1 shows the steps in-
in common organic solvents such as toluene, dichlorometh- volved in this reaction.
ane and tetrahydrofuran. In order to gain further insight
regarding the role of the phosphane in this system, we in-
vestigated the reaction mechanism and possible by-products
involved in this reaction. All attempts to follow the kinetics
of these reactions by means of 1H NMR spectroscopy failed
due to the poor solubility of the elemental chalcogens and
resulting products. However, previous experimental data re-
vealed that the formation of 1 proceeds via the reactive in-
termediate [LAlH(SH)].[2] In order to obtain further insight
into the reaction mechanism, we carried out several experi-
Scheme 1
ments varying the stoichiometry of the starting materials.
The most striking finding was that, in the presence of phos-
As mentioned above, the reaction between [LAlH2] (2)
phane, [LAl(µ-E)2AlL]. analogous to the [LGa(µ-E)2GaL] and elemental sulfur catalyzed by phosphane leads to
(E ϭ O, S) derivatives prepared recently by Power et al.,[26] [LAl(SH)2] (1) and not to the desired [LAl(µ-S)2AlL] (5).[2]
was the only product formed, regardless of the stoichi- Therefore we used the latent protic character of the hydro-
ometry of the reagents employed; the direct reaction of 2 gen atoms from the SH groups of 1 and reacted the latter
with elemental Se (in absence of the phosphane) led entirely species in refluxing toluene with 2. After 15 h we obtained
to the formation of [LAl(SeH)2].[3] In the latter case, an- 5 as a white insoluble microcrystalline solid in 92% yield.
other type of reaction mechanism involving a higher coordi- Scheme 2 summarizes the preparation of the three com-
nated aluminum center formed by complexation of Se2 to pounds.
the aluminum has been suggested.[3,27Ϫ29] Finally, due to
Compounds 3Ϫ5 are insoluble in common organic sol-
the fact that TePR3 compounds are known to be good vents, and the powders obtained after the syntheses yielded
sources of soluble and reactive Te,[30Ϫ32] we carried out the nicely shaped monocrystals from a mixture of toluene/tri-
direct reaction of 2 with TePEt3 in an equimolar ratio. The chloromethane (10:1). The crystallization was achieved by
reaction leads to pure 4 and free PEt3 in almost quantitative solvation of [LAl(µ-E)2AlL] with 2.32 equivalents of tri-
yield, indicating that the gas evolved during the reaction is chloromethane and 0.68 equivalents of toluene (5; E ϭ S),
H2 instead of H2Te. All the experimental results outlined two molecules of trichloromethane and one molecule of
here are highly supportive of the proposed reaction mecha- toluene (3; E ϭ Se), or 2.73 molecules of trichloromethane
nism. Therefore, we assume that Se and Te initially react and 0.27 molecules of toluene (4; E ϭ Te) sharing the same
with the corresponding phosphanes to yield SeP(NMe2)3 spatial position in the crystal lattice, as shown by single-
and TePMe3, respectively. These compounds are crystal X-ray structural analysis (Figures 1Ϫ3).[19]
unstable[30Ϫ32] and react in the following steps with 2 to
The three isostructural compounds crystallize in the
yield [LAlH(EH)] (E ϭ Se, Te), with elimination of phos- monoclinic space group C2/m and possess almost identical
phane. The last step corresponds to the formation of cell parameters (see Table 1). Taking into account the coval-
[33]
˚
˚
[LAl(µ-E)2AlL] (E ϭ Se, Te) by an elimination of two mol- ent radii (1.02 S, 1.17 Se and 1.35 A Te),
the AlϪS
˚
ecules of H2. The splitting of the species into monomer (2.237, 2.245 A), AlϪSe (2.359, 2.370 A) and AlϪTe bonds
units LAlE in the gas phase can indicate an intramolecular (2.575, 2.581 A) are similar to one another. Furthermore,
˚
elimination followed by dimerisation, but we were not able the E(1)ϪAlϪE(1A) angles vary from 96.5° in 5 to 97.9° in
Scheme 2
Eur. J. Inorg. Chem. 2004, 3508Ϫ3512
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 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3509

H. W. Roesky et al.
FULL PAPER
Figure 1. Molecular structure of LAl(µ-S)2AlL (5) with 50%
Figure 3. Molecular structure of LAl(µ-Te)2AlL (4) with 50%
thermal ellipsoids; hydrogen atoms and solvent molecules are
thermal ellipsoids; hydrogen atoms and solvent molecules are
˚
˚
omitted for clarity; selected bond lengths [A] and angles [°]:
omitted for clarity; selected bond lengths [A] and angles [°]:
Al(1)ϪN(1)[N(1A)] 1.928(2), Al(1)ϪS(1) 2.237(1), Al(1)ϪS(1A)
2.245(1), S(1)ϪAl(1)ϪS(1A) 96.5(1), Al(1)ϪS(1)ϪAl(1A) 83.5(1),
N(1)ϪAl(1)ϪN(1A) 94.9(1)
Al(1)ϪN(1)[N(1A)] 1.908(5), Al(1)ϪTe(1) 2.575(3), Al(1)ϪTe(1A)
2.581(2), Te(1)ϪAl(1)ϪTe(1A) 97.9(1), Al(1)ϪTe(1)ϪAl(1A)
82.1(1), N(1)ϪAl(1)ϪN(1A) 96.0(3)
Te) angle is significantly more obtuse than those reported
in the literature (99.9Ϫ103.6° for Se and 102.8Ϫ103.8° for
Te)[4Ϫ12] due to the steric bulk of the β-diketiminato ligand.
The latter values are similar to those of Al4E4 clusters
(94.2Ϫ99.2° for Se and 94.1Ϫ96.3° for Te),[14,15] where the
chalcogen atoms are always coordinated to three aluminum
atoms. The S(1)ϪAlϪS(1A) angle fits within the range of
similar compounds (95.9Ϫ101.9°).[9Ϫ11] Selected bond
lengths and angles for 3Ϫ5 are listed in Table 2.
All three compounds decompose without melting at tem-
peratures above 200 °C, indicating their high thermal sta-
bility. The high stability of compounds 3Ϫ5 is further sup-
ported by the EI-mass spectra, which exhibit [Mϩ] ions for
all three molecules: m/z ϭ 952 (100%) for S, 1048 (48%) for
Se and 1144 (25%) for Te. Unfortunately, due to the low
solubility of 3Ϫ5 we were not able to record NMR spectra.
Conclusion
In summary, we have prepared and structurally charac-
terized three new thermally stable aluminum chalcogenides
[LAl(µ-E)AlL] (E ϭ S, Se, Te). Furthermore, the significant
Figure 2. Molecular structure of LAl(µ-Se)2AlL (3) with 50%
thermal ellipsoids; hydrogen atoms and solvent molecules are
˚
omitted for clarity; selected bond lengths [A] and angles [°]:
Al(1)ϪN(1)[N(1A)] 1.924(3), Al(1)ϪSe(1) 2.359(1), Al(1)ϪSe(1A) influence of the phosphane on the product formation has
2.370(1), Se(1)ϪAl(1)ϪSe(1A) 97.5(1), Al(1)ϪSe(1)ϪAl(1A)
82.5(1), N(1)ϪAl(1)ϪN(1A) 95.2(2)
been demonstrated and a possible mechanism for the con-
version of aluminum hydrides to aluminum selenides and
tellurides outlined.
4 due to the larger radii of the chalcogen atom. All Al2E2
rings are, due to their symmetry, essentially planar, and the
AlϪE bond lengths are analogous to those of similar Al2E2
Experimental Section
˚
˚
species (2.208Ϫ2.248 A for S, 2.221Ϫ2.381 A for Se, and
General: All the reactions and handling of reagents were performed
˚
2.562Ϫ2.588 A for Te), but the E(1)ϪAlϪE(1A) (E ϭ Se, under an atmosphere of dry nitrogen using Schlenk techniques or a
3510
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2004, 3508Ϫ3512

Phosphane-Catalyzed Reactions of LAlH2 with Elemental Chalcogens
FULL PAPER
Table 1. X-ray crystallographic data for 3Ϫ5
3·C7H8·2CHCl3
4·0.27C7H8·2.73CHCl3
5·0.68C7H8·2.32CHCl3
Empirical formula
Molecular mass
Temperature (K)
Crystal system
Space group
C67H92Al2Cl6N4Se2
1378.03
200(2)
monoclinic
C2/m
18.329 (4)
19.161 (5)
11.984 (3)
125.54 (2)
3424.7(14)
2
C62.63H86.9Al2Cl8.18N4Te2
1495.14
100 (2)
monoclinic
C2/m
17.972 (2)
19.125 (2)
11.923 (2)
124.84 (2)
3363.5 (8)
2
C65.08H89.78Al2Cl6.97N4S2
1293.08
100 (2)
monoclinic
C2/m
18.021 (3)
19.107 (3)
11.920 (2)
125.22 (2)
3353.0 (10)
2
˚
a (A)
˚
b (A)
˚
c (A)
β (°)
3
˚
V (A )
Z
Dcalcd. (Mg·mϪ3
)
1.336
0.71073
1.38
1.476
1.54178
10.40
1.281
1.54178
3.84
˚
Wavelength (A)
Absorption coefficient (mmϪ1
)
F(000)
θ range (°)
1436
1520
1369
3.51Ϫ24.99
Ϫ21 Յ h Յ 21
Ϫ4 Յ k Յ 22
Ϫ14 Յ l Յ 14
4065
3.78Ϫ58.10
Ϫ19 Յ h Յ 19
Ϫ18 Յ k Յ 20
Ϫ12 Յ l Յ 12
6352
3.79Ϫ57.76
Ϫ19 Յ h Յ 19
Ϫ20 Յ k Յ 15
Ϫ13 Յ l Յ 13
7081
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-on-fit on F2
Final Rint [I Ͼ 2σ(I)]
3111 (Rint ϭ 0.0307)
3111/111/258
1.076
R1 ϭ 0.0435
wR2 ϭ 0.1083
R1 ϭ 0.0546
wR2 ϭ 0.1171
0.881, Ϫ0.614
2314 (Rint ϭ 0.0356)
2314/405/332
1.126
R1 ϭ 0.0510
wR2 ϭ 0.1174
R1 ϭ 0.0535
wR2 ϭ 0.1187
1.661, Ϫ0.878
2370 (Rint ϭ 0.0224)
2370/285/295
1.146
R1 ϭ 0.0398
wR2 ϭ 0.0989
R1 ϭ 0.0451
wR2 ϭ 0.1017
0.436, Ϫ0.416
Rint (all data)
Ϫ3
˚
Largest different peak and hole (e·A
)
˚
Table 2. Selected bond lengths (A) and angles (°) for 3Ϫ5
3·1 C7H8·2 CHCl3
(E ϭ Se)
4·0.27 C7H8·2.73 CHCl3
(E ϭ Te)
5·0.68 C7H8·2.32 CHCl3
(E ϭ S)
AlϪN
AlϪE(1)
AlϪE(1A)
E(1)ϪAlϪE(1A)
Al(1)ϪEϪAl(1A)
1.924 (3)
2.359 (2)
2.370 (2)
97.5 (1)
1.908 (5)
2.575 (3)
2.581 (2)
97.9 (1)
1.928 (2)
2.237 (1)
2.245 (1)
96.5 (1)
82.5 (1)
82.1 (1)
83.5 (1)
glovebox. Toluene was dried (Na/benzophenone ketyl) and distilled
prior to use. Tellurium (99.5%; Aldrich) and PMe3 (1  solution in
toluene; Fluka) were used as received. P(NMe2)3 (97%; Aldrich)
ν˜ ϭ 3061 vw, 2959 st, 2927 w, 2868 w, 1588 vw, 1544 vst, 1462 w,
1438 m, 1392 vst, 1317 m, 1291 vw, 1249 w, 1177 w, 1101 w, 1058
vw, 1024 w, 937 vw, 867 w, 801 m, 775 vw, 763 w, 539 vw, 463 vw,
was freshly distilled prior to use. Elemental red selenium,[34] 435 w, 411 vw cmϪ1. EI-MS: m/z (%) ϭ 1048 (48) [M]ϩ, 523 (28)
[LAlH2],[3] [LAl(SH)2][2] and TePEt3
ture procedures.
were prepared by litera-
[M/2]ϩ. C58H82Al2N4Se2 (1047.2): calcd. C 66.52, H 7.89, N 5.35;
found C 67.10, H 8.03, N 5.33.
[35]
Infrared spectra were recorded as KBr pellets on a Bio-Rad Digilab
FTS-7 spectrometer in the range 4000Ϫ350 cmϪ1. Mass spectra
were obtained with a Finnigan MAT 8230 or a Varian MAT CH5
instrument (70 eV). Elemental analyses were performed by the
Analytical Laboratory, Institute of Inorganic Chemistry, University
of Goettingen. Melting points were measured in sealed glass tubes
and are uncorrected.
[LAl(µ-Te)2AlL] (4). Method 1: Toluene (20 mL) was added to a
mixture of
2 (1.000 g, 2.239 mmol) and tellurium (0.285 g,
2.230 mmol) and after complete dissolution of 2, PMe3 (0.03 mL,
1  solution in toluene, 0.030 mmol) was added. The reaction mix-
ture was stirred for an additional 15 h, the pale yellow insoluble
product was filtered off, washed with toluene (5 mL) and dried in
vacuo. Yield: 1.15 g (90% based on Te). Decomp. without melting
above 260 °C. IR (KBr pellet): ν˜ ϭ 3061 w, 3024 vw, 2990 w, 2968
vs, 2956 vs, 2930 st, 2866 m, 1587 w, 1543 vs, 1462 vs, 1440 vs, 1394
[LAl(µ-Se)2AlL] (3): Toluene (20 mL) was added to a mixture of 2
(1.000 g, 2.239 mmol) and red selenium (0.176 g, 2.239 mmol) and
after dissolution of 2, freshly distilled P(NMe2)3 (0.03 mL, vs, 1365 sh, 1300 m, 1251 s, 1176 m, 1100 m, 1057 m, 1024 m, 937
0.055 mmol) was added. The reaction mixture was stirred for an
additional 16 h and the white insoluble product was filtered off,
washed with toluene (5 mL) and dried in vacuo. Yield: 1.07 g
(91%). Decomp. without melting above 260 °C. IR (KBr pellet):
m, 942 w, 868 st, 798 vs, 780 m, 761 st, 708 vw, 648 w, 595 vw, 537
w, 447 vw, 417 vst cmϪ1. EI-MS: m/z (%) ϭ 1144 (25) [M]ϩ, 574
(60) [M/2]ϩ, 443 (100) [M/2 Ϫ Te Ϫ H]ϩ. C58H82Al2N4Te2 (1144.5):
calcd. C 60.87, H 7.22, N 4.90; found C 60.50, H 7.15, N 4.82.
Eur. J. Inorg. Chem. 2004, 3508Ϫ3512
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 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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H. W. Roesky et al.
FULL PAPER
[8]
[9]
P. D. Godfrey, C. L. Raston, B. W. Skelton, V.-A. Tolhurst, A.
H. White, Chem. Commun. 1997, 2235Ϫ2236.
C. Schnitter, A. Klemp, H. W. Roesky, H.-G. Schmidt, C.
Röpken, R. Herbst-Irmer, M. Noltemeyer, Eur. J. Inorg. Chem.
1998, 2033Ϫ2039.
A. Ecker, R. Köppe, C. Üffing, H. Schnöckel, Z. Anorg. Allg.
Chem. 1998, 624, 817Ϫ822.
Method 2: Toluene (20 mL) was added to a mixture of 2 (1.000 g,
2.239 mmol) and TePEt3 (0.550 g, 2.239 mmol) and the reaction
mixture was stirred for an additional 2 h. The pale-yellow insoluble
product was filtered off, washed with toluene (5 mL) and dried in
vacuo. Yield: 1.22 g (95%).
[10]
[11]
[12]
[13]
[14]
[15]
[LAl(µ-S)2AlL] (5): Toluene (20 mL) was added to a mixture of 1
(1.144 g, 2.239 mmol) and 2 (1.000 g, 2.239 mmol) and the reaction
mixture was refluxed over a period of 15 h. After this time, the
mixture was cooled to ambient temperature and a white insoluble
product was filtered off, washed with toluene (5 mL) and dried in
vacuo. Yield: 1.96 g (92%). Decomp. without melting above 200 °C.
IR (KBr pellet): ν˜ ϭ 3062 vw, 2959 st, 2924 m, 2866 w, 1589 vw,
1547 vst, 1529 sh, 1462 m, 1437 m, 1390 vst, 1317 st, 1291 vw, 1249
m, 1176 w, 1100 vw, 1058 vw, 1024 w, 937 vw, 868 w, 801 m, 775
w, 763 w, 652 vw, 541 w, 516 m, 472 w, 454 m cmϪ1. EI-MS: m/z
(%) ϭ 952 (100) [M]ϩ, 937 (64) [M Ϫ CH3]ϩ, 909 (21) [M Ϫ
C3H7]ϩ, 477 (58) [M/2]ϩ. C58H82Al2N4S2 (953.40): calcd. C 73.07,
H 8.67, N 5.88; found C 72.63, H 8.53, N 5.88.
R. J. Wehmschulte, P. P. Power, Chem. Commun. 1998,
335Ϫ336.
H. Zhu, J. Chai, H. W. Roesky, M. Noltemeyer, H.-G. Schmidt,
D. Vidovic, J. Magull, Eur. J. Inorg. Chem. 2003, 3113Ϫ3119.
K. S. Klimek, J. Prust, H. W. Roesky, M. Noltemeyer, H.-G.
Schmidt, Organometallics 2001, 20, 2047Ϫ2051.
C. F. Harlan, E. G. Gillan, S. G. Bott, A. R. Barron, Or-
ganometallics 1996, 15, 5479Ϫ5488.
S. Schulz, H. W. Roesky, H. J. Koch, G. M. Sheldrick, D.
Stalke, A. Kuhn, Angew. Chem. 1993, 105, 1828Ϫ1830; Angew.
Chem. Int. Ed. Engl. 1993, 32, 1729Ϫ1731.
A. H. Cowley, R. A. Jones, P. R. Harris, D. A. Atwood, L.
Contreras, C. J. Burek, Angew. Chem. 1991, 103, 1164Ϫ1166;
Angew. Chem. Int. Ed. Engl. 1991, 30, 1143Ϫ1146.
T. Hirabayashi, K. Inoue, K. Yokota, Y. Ishii, J. Organomet.
Chem. 1975, 92, 139Ϫ145.
G. H. Robinson, M. F. Self, W. T. Pennington, S. A. Sango-
koya, Organometallics 1988, 7, 2424Ϫ2426.
R. J. Wehmschulte, P. P. Power, J. Am. Chem. Soc. 1997, 119,
9566Ϫ9567.
W. Uhl, A. Vester, J. Organomet. Chem. 1993, 443, 9Ϫ17.
W. Uhl, R. Gerding, I. Hahn, S. Pohl, W. Saak, H. Reuter,
Polyhedron 1996, 15, 3987Ϫ3992.
W. Uhl, U. Schuetz, Z. Naturforsch., Teil B 1994, 49, 931Ϫ934.
W. Zheng, H. Hohmeister, N. C. Mösch-Zanetti, H. W. Roesky,
M. Noltemeyer, H.-G. Schmidt, Inorg. Chem. 2001, 40,
2363Ϫ2367.
W. Zheng, N. C. Mösch-Zanetti, H. W. Roesky, M. Noltemeyer,
M. Hewitt, H.-G. Schmidt, T. R. Schneider, Angew. Chem.
2000, 112, 4446Ϫ4449; Angew. Chem. Int. Ed. 2000, 39,
4276Ϫ4279.
M. Witt, H. W. Roesky, Curr. Sci. 2000, 78, 410Ϫ430.
N. J. Hardman, P. P. Power, Inorg. Chem. 2001, 40, 2474Ϫ2475.
C. Jones, G. A. Koutsantonis, C. L. Raston, Polyhedron 1993,
12, 1829Ϫ1848.
C. L. Raston, J. Organomet. Chem. 1994, 475, 15Ϫ24.
M. G. Gardiner, C. L. Raston, V.-A. Tolhurst, J. Chem. Soc.,
Chem. Commun. 1995, 1457Ϫ1458.
[16]
[17]
[18]
[19]
X-ray Crystallographic Study: Data for the X-ray structures of
[LAl(µ-S)2AlL] and [LAl(µ-Te)2AlL] were collected on a Bruker
three-circle diffractometer equipped with a SMART 6000 CCD
area-detector, whereas data for the X-ray structural analysis of
[LAl(µ-Se)2AlL] were collected on a Stoe-AED 2 four-circle dif-
fractometer. Structures were solved by direct methods (SHELXS-
97)[36] and refined by full-matrix least-squares methods on F2 with
SHELXL-97.[37] The non-hydrogen atoms were refined aniso-
tropically; hydrogen atoms were included at geometrically idealized
positions and refined with the riding model.
CCDC-228825 (for 5), -228826 (for 3), -228827 (for 4) contain the
supplementary crystallographic data for this paper. These data can
be obtained free of charge at www.ccdc.cam.ac.uk/conts/
retrieving.html [or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: ϩ 44-
1223-336033; E-mail: deposit@ccdc.cam.ac.uk].
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
Acknowledgments
We thank the Deutsche Forschungsgemeinschaft, the Göttinger
Akademie der Wissenschaften and the Fonds der Chemischen In-
dustrie (predoctoral fellowship to V. J.) for funding.
[28]
[29]
[30]
[31]
[32]
[33]
M. L. Steigerwald, C. R. Sprinkle, Organometallics 1988, 7,
245Ϫ246.
L.-B. Han, F. Mirzaei, M. Tanaka, Organometallics 2000, 19,
[1]
G. Bai, Y. Peng, H. W. Roesky, J. Li, H.-G. Schmidt, M. Nolte-
722Ϫ724.
meyer, Angew. Chem. 2003, 115, 1164Ϫ1167; Angew. Chem. Int.
N. Kuhn, G. Henkel, H. Schumann, R. Fröhlich, Z. Natur-
forsch., Teil B 1990, 45, 1010Ϫ1018.
J. E. Huheey, Inorganic Chemistry: Principles of Structure and
Reactivity, Harper Collins College Publishers, New York, 1993,
p. 292.
Ed. 2003, 42, 1132Ϫ1135.
V. Jancik, Y. Peng, H. W. Roesky, J. Li, D. Neculai, A. M.
[2]
Neculai, R. Herbst-Irmer, J. Am. Chem. Soc. 2003, 125,
1452Ϫ1453.
[3]
[34]
[35]
C. Cui, H. W. Roesky, H. Hao, H.-G. Schmidt, M. Noltemeyer,
J. Meyer, Ber. 1913, 46, 3089Ϫ3091.
Angew. Chem. 2000, 112, 1885Ϫ1887; Angew. Chem. Int. Ed.
R. A. Zingaro, B. H. Steeves, K. Irgolic, J. Organomet. Chem.
1965, 4, 320Ϫ323.
2000, 39, 1815Ϫ1817.
C. Cui, H. W. Roesky, H.-G. Schmidt, M. Noltemeyer, Or-
[4]
[36]
[37]
G. M. Sheldrick, SHELXS-97, Program for Structure Solution,
Acta Crystallogr., Sect. A 1990, 46, 467Ϫ473.
G. M. Sheldrick, SHELXL-97, Program for Crystal Structure
Refinement, University of Göttingen, Göttingen, Germany,
1997.
ganometallics 1999, 18, 5120Ϫ5123.
C. Cui, H. W. Roesky, H.-G. Schmidt, M. Noltemeyer, Inorg.
[5]
Chem. 2000, 39, 3678Ϫ3681.
W. J. Grigsby, C. L. Raston, V.-A. Tolhurst, B. W. Skelton, A.
[6]
H. White, J. Chem. Soc., Dalton Trans. 1998, 2547Ϫ2556.
M. G. Gardiner, C. L. Raston, V.-A. Tolhurst, J. Chem. Soc.,
Received January 23, 2004
[7]
Early View Article
Chem. Commun. 1995, 2501Ϫ2502.
Published Online June 23, 2004
3512
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Eur. J. Inorg. Chem. 2004, 3508Ϫ3512