Preparation of [LAI-(μ-S)2MCp2] (M = Ti, Zr) from the structurally characterized lithium completes [{LAl(SH)[SLi(thf) 2]}2] and [{LAI[SLi)2(thf)3] ·2-THF

Article abstract of DOI:10.1002/anie.200461254

Sulfur bridges: The reactions of [LAI(SH)₂] (L = HC(CMeNAr) ₂, Ar= 2,6-iPr₂C₆H₃) with LiN(SiMe₃)₂ in molar ratio 1:2 and 1:1, respectively, lead to species with the formula [{LAl

Full text of DOI:10.1002/anie.200461254

Communications
Mixed-Metal Compounds
Preparation of [LAl(m-S)2MCp2] (M = Ti, Zr)
from the Structurally CharacterizedLithium
Complexes [{LAl(SH)[SLi(thf)2]}2] and
[{LAl[(SLi)2(thf)3]}2]·2THF**
Vojtech Jancik, Herbert W. Roesky,* Dante Neculai,
Ana M. Neculai, and Regine Herbst-Irmer
Dedicated to Professor Hubert Schmidbaur
on the occasion of his 70th birthday
Recently, we reported the preparation of the unique mono-
meric [LAl(SH)2] (1) (L = HC(CMeNAr)2; Ar= 2,6-
iPr2C6H3) comprising two terminal SH moieties.[1] This
unusual species led us to explore the substitution pattern of
the SH protons, their exchange with transition metals would
open a new route for the preparation of heterobimetallic
sulfides containing aluminum. To date very few examples with
aluminum bridging sulfide are known. Such species include
[(tBuAl)(tBuAlMe)2(m3-S)3ZrCp2] (Cp = C5H5), prepared by
degradation of the [{tBuAl(m3-S)}4] cage with two equivalents
of [Cp2ZrMe2].[2] Moreover, there are known aluminum
sulfides with [AlS]n core, which can be either planar (n = 2),
cubic (n = 4), drum (n = 6), or possess more complex struc-
tures with an Al:S molar ratio different from 1:1.[3]
Attempts to prepare heterobimetallic sulfides with 1 and
ZnMe2 or CdMe2 through alkane elimination failed, in spite
of the high affinity of these elements towards chalcogens.[4]
We observed even at low temperature only the formation of
an inseparable mixture of products and the free ligand. This
situation is in contrast to the successful preparation of [LAl(m-
S)2AlL] from 1 and [LAlH2].[3] Following the protocol of Nöth
et al. on the preparation of aluminum–lithium salts from
LiAlH4 and thiols,[5] we chose the lithiation of 1 with MeLi
and nBuLi in diethyl ether or THF as an alternative route to
the desired compounds. Unfortunately, under the given
conditions the decomposition of 1 was observed. However,
the difficulties encountered in the preparation of the
dilithium salt [{LAl[(SLi)2(thf)3]}2]·2THF (2) were overcome
by direct reaction of 1 with two equivalents of LiN(SiMe3)2 in
THF at 08C. The extremely sensitive pale yellow product 2 is
a dimer solvated by eight molecules of THF as demonstrated
by X-ray structural analysis. It has low solubility in THF and
forms a microcrystalline precipitate within a few seconds of
starting materials being mixed. The recovery of the crystals
[*] Dipl.-Chem. V. Jancik, Prof. Dr. H. W. Roesky, Dr. D. Neculai,
Dr. A. M. Neculai, Dr. R. Herbst-Irmer
Institut für Anorganische Chemie
Georg-August Universität
Tammannstrasse 4, 37077 Göttingen (Germany)
Fax: (+49)551-39-3373
E-mail: hroesky@gwdg.de
[**] This work was supported by the Deutsche Forschungsgemeinschaft
and the Göttinger Akademie der Wissenschaften. V.J. thanks the
Fonds der Chemischen Industrie for the predoctoral fellowship.
L=HC(CMeNAr)2, A r=2,6-iPr2C6H3; Cp=C5H5).
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was performed within 15 min of the addition of the solvent to
avoid decomposition caused by free HN(SiMe3)2. However,
compound 2 loses THF upon drying in vacuo, leading to a
dimeric product [{LAl[(SLi)2(thf)2]}2] (2’) containing only
[LAl(SH)(m-S)M(Cl)Cp2], followed by a translithiation with a
second molecule of 3, yielding and [LAl(SLi)(m-
1
S)M(Cl)Cp2]. Subsequently, [LAl(SLi)(m-S)M(Cl)Cp2] under-
goes an intramolecular elimination of LiCl to yield [LAl(m-
S)2MCp2]. A second possible mechanism is an in situ for-
mation of [{LAl(SH)(m-S)}2MCp2] followed by its rapid
rearrangement to yield 1 and 4 (or 5) (Scheme 1).
X-ray quality crystals of 2 and 3 were obtained by slow
cooling their THF solutions.[6] Both derivatives crystallize in
the monoclinic space group P21/n as pale yellow crystals.
Compound 3 shows a simple coordination environment for
the Li atoms [LAl(SH)(m3-S)(m-Li·2THF)2(m3-S)Al(SH)L],
while the structure of 2 is more complex and none of the four
lithium atoms are equivalent. As depicted in Figure 1, the
lithium atoms Li(1), Li(2) and Li(4) are coordinated by two,
one, and three THF molecules, respectively, whereas Li(3) is
not coordinated to THF. This diversity is due to the steric bulk
of the ligand L.
1
four molecules of THF as determined by H NMR spectros-
copy. This final product proved to be stable upon storage for
several months under an inert atmosphere. After the success-
ful isolation of 2’, we became interested in the preparation of
the monolithium salt [{LAl(SH)[SLi(thf)2]}2] (3). To our
knowledge such systems are not known for any kind of
metal and, could be precursors for substitution reactions. For
the preparation of 3 a similar method was used as for 2’. After
removal of all volatiles in vacuo compound 3 was isolated in
84% yield. Moreover, no decomposition was detected in the
presence of HN(SiMe3)2 or during the removal of the solvent,
thus demonstrating a higher stability of 3 compared to that of
2. As expected, 3 has a dimeric arrangement in the solid state,
with each lithium coordinated to two molecules of THF and
two sulfur atoms. The amount of THF in 3 remains unchanged
even after keeping 3 for several hours in vacuo (Scheme 1).
Figure 1. Molecular structure of [{LAl[(SLi)2(thf)3]}2]·2THF (2); thermal
ellipsoids set at 50% probability. All hydrogen atoms, noncoordinated
THF molecules and carbon atoms of the coordinating THF molecules
are omitted for clarity. Selected bond lengths [Š] and angles [8]: Al(1)-
S(1) 2.186(1), Al(1)-S(2) 2.182(1), Al(2)-S(3) 2.173(1), Al(2)-S(4)
2.181(1), Li(1)-S(1) 2.482(2), Li(1)-S(3) 2.414(2), Li(2)-S(1) 2.544(2),
Li(2)-S(3) 2.449(2), Li(2)-S(4) 2.565(2), Li(3)-S(1) 2.502(2), Li(3)-S(2)
2.345(2), Li(3)-S(4) 2.323(2), Li(4)-S(2) 2.343(3); S(1)-Al(1)-S(2)
111.6(1), S(3)-Al(2)-S(4) 113.0(1), Al(1)-S(1)-Li(1) 149.6(1), Al(1)-S(1)-
Li(2) 126.3(1), Al(1)-S(1)-Li(3) 74.3(1), Al(1)-S(2)-Li(3) 77.7(1), Al(1)-
S(2)-Li(4) 152.1(1), Al(2)-S(3)-Li(1) 114.8(1), Al(2)-S(3)-Li(2) 76.3(1),
Al(2)-S(4)-Li(2) 73.7(1), Al(2)-S(4)-Li(3) 118.0(1), Li(1)-S(1)-Li(2)
68.2(1), Li(1)-S(1)-Li(3) 92.5(1), Li(1)-S(3)-Li(2) 70.8(1), Li(2)-S(1)-
Li(3) 66.0(1), Li(2)-S(4)-Li(3) 68.2(1), Li(3)-S(2)-Li(4) 116.8 (1), S(1)-
Li(1)-S(3) 112.1(1), S(1)-Li(2)-S(3) 108.9(1), S(1)-Li(2)-S(4) 107.8(1),
S(1)-Li(3)-S(2) 96.4(1), S(1)-Li(3)-S(4) 117.6(1), S(2)-Li(3)-S(4)
134.6(1), S(3)-Li(2)-S(4) 92.8(1).
Scheme 1. Synthesis of compounds 2’–5.
We focused on reactivity studies of 2’ and 3 towards the
transition-metal halides, namely [Cp2TiCl2] and [Cp2ZrCl2].
When a solution of [Cp2MCl2] (M = Ti, Zr) in THF was added
dropwise to the solution of 2’ in THF at À208C, the color of
the resulting mixture became brownish-green, M = Ti, and
deep yellow for M = Zr. After removal of the THF, extraction
of the crude product with toluene and several purification
steps, compounds [LAl(m-S)2MCp2] (M = Ti (4), M = Zr (5))
were isolated in 89% and 85% yield, respectively.
Surprisingly the reaction of
3 with [Cp2TiCl2] or
[Cp2ZrCl2] in a molar ratio 2:1 does not yield the expected
[{LAl(SH)S}2MCp2] but rather a mixture of 1 and 4 (or 5) is
formed. This result suggests that the formation of the four-
The two THF molecules coordinated to Li(1) require
there to be more space between the 2,6-iPr2C6H3 moieties of L
and thus force the substituents on the opposite side closer
together. This steric pressure results in Li(4) being pushed out
of the central area of the dimer. Subsequently the coordina-
tion of three THF molecules covers the unsaturated sites on
Li(4). For the two remaining Li atoms, the situation is similar.
membered ring [LAl(m-S)2MCp2] is preferred over
a
LAl(SH)-S-M(Cp)2-S-Al(SH)L chain arrangement contain-
ing free SH groups. One pathway for the formation of 1 and 4
(or 5) in the above reaction may involve the intermediate
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Li(2) can still be coordinated by one THF molecule whereas
Li(3) is coordinated only to three sulfur atoms. These
different coordination sites of lithium atoms are compensated
À
by the variation of the Li S bond lengths (2.323–2.565 Š).
The Al2S4Li4 core can also be described as being a six-
membered AlS3Li2 ring with alternating sulphur and metal
atoms, which is capped by another lithium atom and a bent
Al-S-Li unit is joined to one of the S–Li edges of this
hexagonal pyramid to form a condensed four-membered
À
AlS2Li ring. The shortness of the S(4) Li(3) bond (2.323 Š) is
caused by the unsaturated coordination sphere of Li(3) which
contains only three sulfur atoms and is one of the shortest
[7a–c]
À
À
S Li bonds observed to date.
All the other S Li bonds of
2 (2.343–2.565 Š) and 3 (2.424 and 2.478 Š) are in the range
observed for similar species (2.327–2.964 Š).[5,7] Figure 2
shows the molecular structure of 3 in which the S2Li2 core is
essentially planar owing to the crystal symmetry.
Figure 3. Molecular structure of [LAl(m-S)2TiCp2] (4); thermal ellipsoids
set at 50% probability. All hydrogen atoms are omitted for clarity.
Selected bond lengths [Š] and angles [8]: Al(1)-N(1) 1.918(2), Al(1)-
N(2) 1.921(2), Al(1)-S(1) 2.208(1), Al(1)-S(2) 2.197(1), Ti(1)-S(1)
2.416(1), Ti(1)-S(2) 2.473(1), Ti(1)-XCp1 2.091(3), Ti(1)-XCp2 2.090(3);
S(1)-Al(1)-S(2) 102.5(1), Al(1)-S(1)-Ti(1) 84.7(1), Al(1)-S(2)-Ti(1)
83.6(1), S(1)-Ti(1)-S(2) 89.3(1), XCp1-Ti(1)-XCp2 130.0(2); X=centroid of
Cp ring.
À
Ti S, 2.059–2.093 Š for XCp–Ti, 129.6–131.68 for XCp1-Ti-XCp2
and 86.5–95.98 for S-Ti-S).[8] The substitution of the SH
À
protons by Li or Ti has a significant influence on the Al S
À
bond length. The Al S bond lengths decrease in the series
from 1 (2.223 Š and 2.217 Š)[1] to 4 (2.208 and 2.197 Š), to 2
(2.173–2.186 Š) and finally to 3 (2.123 Š). The partial
negative charge on the substituted S atom in 3 causes a
À
shortening of the Al S bond and thus, increases the electron
density on the aluminum center resulting in an elongation of
À
Figure 2. Molecular structure of [{LAl(SH)[SLi(thf)2]}2] (3); thermal
ellipsoids set at 50% probability. All hydrogen atoms (except those of
the Al S(H) bond (2.268 Š).
In summary, we have developed a new strategy for the
preparation of heterobimetallic sulfides containing aluminum
and isolated four new species. Furthermore, the lithium salts
[{LAl[(SLi)2(thf)2]}2] and [{LAl(SH)[SLi(thf)2]}2] are promis-
ing precursors for further reactions.
À
the S H moieties), and the carbon atoms of the THF molecules are
omitted for clarity. Selected bond lengths [Š] and angles [8]: Al(1)-N(1)
1.928(2), Al(1)-N(2) 1.935(2), Al(1)-S(1) 2.268(1), Al(1)-S(2) 2.123(1),
H(1)-S(1) 1.28(5), Li(1)-S(2) 2.478(5), Li(1)-S(2A) 2.424(5); S(1)-Al(1)-
S(2) 115.7(1), Al(1)-S(2)-Li(1) 151.6(1), Al(1)-S(2)-Li(1A) 111.7(1),
Li(1)-S(2)-Li(1A) 78.0(2), S(2)-Li(1)-S(2A) 102.0(2).
Experimental Section
This S2Li2 motif can be found in many substances
containing these two elements including 2.[5,7] The free SH
groups are not involved in any kind of hydrogen bonding and
are orientated trans to each other.
Crystals of 4 were obtained by slow cooling of its toluene/
hexane solution.[6] 4 crystallizes in the monoclinic space group
P21 and its molecular structure is shown in Figure 3.
The AlS2Ti ring is essentially planar with the sum of inner
angles of 3608. The widest angle (102.58) corresponds to that
at the aluminum center, while the one at the titanium center is
almost a right angle (89.38). The Ti–XCp separations (XCp is
the centroid of the Cp group) are 2.091 and 2.090 Š and the
All manipulations were performed under a dry and oxygen-free
atmosphere (N2 or Ar) using Schlenk-line and glovebox techniques.
2’: Compound 1 (2.000 g, 3.916 mmol) and LiN(SiMe3)2 (1.311 g,
7.832 mmol) were mixed as solids in a flask and subsequently cold
THF (70 mL, 08C) was added. Within a few seconds pale yellow
crystals of 2 started to precipitate from the reaction mixture. After
5 min of stirring at 08C, the reaction mixture was cooled to À208C
and maintained at this temperature for 5–-10 min under vigorous
stirring to support the crystallization. The time allowed for the
crystallization is determined by the color of the solution. The original
pale yellow color of the solution turned slowly into a dark brown,
which indicates decomposition of the product. Thus, the filtration of
the microcrystalline product should occur within the first significant
color change of the mother liquor. After washing the crude product
with cold THF (5 mL) and drying in vacuo, 2’ was obtained as a pale
X
Cp1-Ti-XCp2 angle is 1308. All these data are in good
1
agreement with those reported for [Cp2Ti(m-S)2ML’L’’] (e.g.
M = Si, Ti, Ru, L’ = Cp, L’’ = Cl) species (2.425–2.458 Š for
yellow powder. Yield 2.19 g (84%). M.p. 3208C (decomp). H NM R
(500 MHz, [D8]THF, 258C, TMS): d = 1.07 (d, 3J(H,H) = 6.8 Hz, 24H,
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Chemie
CH(CH3)2), 1.25 (d, 3J(H,H) = 6.8 Hz, 24H, CH(CH3)2), 1.51 (s, 12H,
CH3), 1.77 (m, 16H, O(CH2CH2)2), 3.62 (m, 16H, O(CH2CH2)2), 4.00
(sept, 3J(H,H) = 6.8 Hz, 8H, CH(CH3)2), 5.01 (s, 2H, CH), 7.00–
7.01 ppm (m, 12H, m-, p- Ar(H)); 13C NMR (125.8 MHz, [D8]THF,
258C, TMS): d = 24.7 (CH(CH3)2), 24.8 (CH(CH3)2), 26.4
(O(CH2CH2)2), 27.4 (CH(CH3)2), 28.7 (CH3), 68.2 (O(CH2CH2)2),
Elemental analysis calcd (%) for C39H51AlN2S2Zr (730.17): C 64.15, H
7.04, N 3.84; found: C 63.09, H 7.30, N 3.83.
Received: July 9, 2004
Keywords: aluminum · bridging ligands · sulfur · titanium ·
.
98.1 (g-CH), 124.2, 126.2, 145.1, 146.1 (i-, o-, m-, p-C of Ar),
zirconium
7
=
168.1 ppm (C N); Li NMR (116.6 MHz, [D8]THF, 258C, LiCl, 1m in
D2O): d = 1.26 (SLi). Elemental analysis calcd (%) for C74H114Al2Li4-
N4O4S4 (1333.71): C 66.64, H 8.62, N 4.20; found: C 65.70, H 8.57, N
4.27.
[1] V. Jancik, Y. Peng, H. W. Roesky, J. Li, D. Neculai, A. M.
Neculai, R. Herbst-Irmer, J. Am. Chem. Soc. 2003, 125, 1452 –
1453.
3: Compound 1 (1.000 g, 1.958 mmol) and LiN(SiMe3)2 (0.328 g,
1.958 mmol) were mixed as solids in a flask and subsequently THF
(30 mL) was added at ambient temperature. The mixture was stirred
for 5 min, all the volatiles were removed in vacuo. The crude product
was washed with cold hexane (5 mL) to remove the remaining
HN(SiMe3)2, yielding 3 as a pale yellow powder. Yield 1.11 g (85%).
[2] C. J. Harlan, A. R. Barron, J. Cluster Sci. 1996, 7, 455 – 467.
[3] a) V. Jancik, M. M. Moya Cabrera, H. W. Roesky, R. Herbst-
Irmer, D. Neculai, A. M. Neculai, M. Noltemeyer, H.-G.
Schmidt, Eur. J. Inorg. Chem. 2004, 3508 – 3512, and references
therein; b) Y. Peng, H. Fan, V. Jancik, H. W. Roesky, R. Herbst-
Irmer, Angew. Chem. 2004, 116, 6316–6318; Angew. Chem. Int.
Ed. 2004, 43, 6190–6192
[4] N. N. Greenwood, A. Earnshaw, Chemistry of the Elements;
Butterworth-Heinemann, Oxford, U.K., 2002, pp. 1205 – 1210.
[5] J. Knizek, H. Nöth, A. Schlegel, Eur. J. Inorg. Chem. 2001, 181 –
187.
1
M.p. 2308C (decomp). H NMR (500 MHz, [D8]THF, 258C, TMS):
3
d = À1.00 (s, 2H, SH), 1.04 (d, J(H,H) = 6.8 Hz, 12H, CH(CH3)2),
1.21 (d, 3J(H,H) = 6.8 Hz, 12H, CH(CH3)2), 1.25 (d, 3J(H,H) = 6.8 Hz,
12H, CH(CH3)2), 1.40 (d, 3J(H,H) = 6.8 Hz, 12H, CH(CH3)2), 1.69 (s,
12H, CH3), 1.77 (m, 16H, O(CH2CH2)2), 3.62 (m, 16H,
O(CH2CH2)2), 3.77 (sept, 3J(H,H) = 6.8 Hz, 4H, CH(CH3)2), 3.85
(sept, 3J(H,H) = 6.8 Hz, 4H, CH(CH3)2), 5.13 (s, 2H, CH), 7.06–
7.16 ppm (m, 12H, m-, p-Ar–H); 13C NMR (125.8 MHz, [D8]THF,
258C, TMS): d = 24.3 (CH(CH3)2), 24.4 (CH(CH3)2), 25.1
(CH(CH3)2), 25.1 (CH(CH3)2), 26.4 (O(CH2CH2)2), 28.0
(CH(CH3)2), 28.5 (CH(CH3)2), 29.6 (CH3), 68.2 (O(CH2CH2)2), 97.6
(g-CH), 124.1, 134.3, 126.4, 143.6, 145.7, 146.0 (i-, o-, m-, p-C of Ar),
169.0 ppm (C = N); 7Li NMR (116.6 MHz, [D8]THF, 258C, LiCl, 1m in
D2O) d = 0.32 (SLi). IR(KBr pellet): 2552 vw (SH) cmÀ1. Elemental
analysis calcd (%) for C74H116Al2Li2N4O4S4 (1321.84): C 67.24, H 8.85,
N 4.24; found: C 66.45, H 8.45, N 4.52.
[6] Crystal data for 2: C90H146Al2Li4N4O8S4, Mr = 1622.07, mono-
clinic, space group P21/n, a = 22.746(1), b = 16.414(1), c =
26.111(1) Š, b = 106.45(1)8, V= 9350(1) Š3, Z = 4, 1calcd
=
1.152 MgmÀ3
,
F(000) = 3520, l = 1.54178 Š, T= 100(2) K,
Of the 50723 measured reflections,
m(CuKa) = 1.525 mmÀ1
.
13679 were independent (Rint = 0.0214). The final refinements
converged at R1 = 0.0288 for I > 2s(I), wR2 = 0.0747 for all data.
The final difference Fourier synthesis gave a min/max residual
electron density of À0.187/ + 0.250 eŠÀ3; crystal data for 3:
C74H116Al2Li2N4O4S4, Mr = 1321.78, monoclinic, space group P21/
n, a = 12.558(1), b = 19.423(1), c = 16.862(1) Š, b = 111.29(1)8,
V= 3832(1) Š3, Z = 2, 1calcd = 1.145 MgmÀ3, F(000) = 1432, l =
1.54178 Š, T= 100(2) K, m(CuKa) = 1.721 mmÀ1. Of the 14831
measured reflections, 5403 were independent (Rint = 0.0567).
The final refinements converged at R1 = 0.0441 for I > 2s(I),
wR2 = 0.1219 for all data. The final difference Fourier synthesis
gave a min/max residual electron density of À0.238/ + 0.277
eŠÀ3; crystal data for 4: C39H51AlN2S2Ti, Mr = 686.82, mono-
clinic, space group P21, a = 11.831(1), b = 8.727(1), c =
4: A solution of [Cp2TiCl2] (0.224 g, 0.900 mmol) in THF (20 mL)
was added dropwise to a solution of 2’ (0.600 g, 0.450 mmol) in THF
(40 mL) at À208C. During the addition, the color of the solution
changed to deep brown-green. After the addition was complete, the
reaction mixture was stirred for additional 5 min at À208C and than
allowed to warm to ambient temperature. The solvent was removed
in vacuo and the crude product was extracted twice with cold toluene
(15 mL, 58C). After filtration, removing of the toluene from the
filtrate, washing of the product with a cold toluene:pentane (5 mL,
1:4) mixture and drying in vacuo, 4 was obtained as a brown-green
powder. Yield 0.55 g (89%). Decomposition without melting at
2708C. 1H NMR (500 MHz, C6D6, 258C, TMS): d = 1.06 (d, 3J(H,H) =
6.8 Hz, 12H, CH(CH3)2), 1.64 (s, 6H, CH3), 1.88 (d, 3J(H,H) = 6.8 Hz,
17.776(1) Š, b = 99.10(1)8, V= 1812(1) Š3, Z = 2, 1calcd
1.259 MgmÀ3
F(000) = 732, l = 1.54178 Š, T= 100(2) K,
=
,
m(CuKa) = 3.525 mmÀ1. Of the 6417 measured reflections, 3178
were independent (Rint = 0.0189). The final refinements con-
verged at R1 = 0.0235 for I > 2s(I), wR2 = 0.0591 for all data and
the absolute structure parameter was refined to 0.013(5). The
final difference Fourier synthesis gave a min/max residual
electron density of À0.199/ + 0250 eŠÀ3. Data for the structures
were collected on a Bruker three-circle diffractometer equipped
with a SMART 6000 CCD detector. Intensity measurements
were performed on a rapidly cooled crystal (0.3 ” 0.2 ” 0.1 mm3)
in the range 4.56 ꢀ 2q ꢀ 120.088 (2), (0.2 ” 0.1 ” 0.1 mm3) in the
range 7.24 ꢀ 2q ꢀ 118.028 (3), and (0.5x0.2x0.2 mm3) in the
range 8.40 ꢀ 2q ꢀ 113.688 (4). The structures were solved by
direct methods (SHELXS-97[9]) and refined against all data by
3
12H, CH(CH3)2), 3.57 (sept, J(H,H) = 6.8 Hz, 4H, CH(CH3)2), 4.84
(s, 1H, CH), 5.71 (s, 10H, C5H5), 7.30(-7.37 ppm (m, 6H, m-, p-
Ar(H)); 13C NMR (125.8 MHz, C6D6, 258C, TMS): d = 24.0
(CH(CH3)2), 25.7 (CH(CH3)2), 25.7 (CH(CH3)2), 29.1 (CH3), 94.9
(g-CH), 118.3 (C5H5), 125.0, 128.0, 140.6, 146.0 (i-, o-, m-, p-C of Ar),
=
170.2 ppm (C N); 27Al NMR (78.2 MHz, C6D6, 258C, [Al(H2O)6]3+
)
d = 94 ppm. MS (70 eV): m/z (%): 686 (8) [M+], 621 (100) [M+(Cp].
Elemental analysis calcd (%) for C39H51AlN2S2Ti (686.83): C 68.20, H
7.48, N 4.08; found: C 67.61, H 7.46, N 4.02.
5: preparation like that of
4 from [Cp2ZrCl2] (0.263 g,
0.900 mmol) and 2’ (0.600 g, 0.450 mmol). The product was isolated
as a deep yellow powder. Yield 0.56 g (85%). Decomposition without
melting at 1808C. 1H NMR (500 MHz, C6D6, 258C, TMS): d = 1.06 (d,
3J(H,H) = 6.8 Hz, 12H, CH(CH3)2), 1.65 (s, 6H, CH3), 1.82 (d,
3J(H,H) = 6.8 Hz, 12H, CH(CH3)2), 3.59 (sept, 3J(H,H) = 6.8 Hz, 4H,
CH(CH3)2), 4.87 (s, 1H, CH), 5.65 (s, 10H, C5H5), 7.22–7.32 ppm (m,
6H, m-, p-Ar(H)); 13C NMR (125.8 MHz, C6D6, 258C, TMS): d = 24.4
(CH(CH3)2), 25.7 (CH(CH3)2), 25.7 (CH(CH3)2), 29.0 (CH3), 95.1 (g-
CH), 114.4 (C5H5), 124.9, 128.0, 140.1, 146.1 (i-, o-, m-, p-C of Ar),
=
full-matrix least-squares on F2[10]. The hydrogen atoms of C H
À
bonds were placed in idealized positions, whereas the hydrogen
atom from the SH moiety in 3 was localized from the difference
electron-density map and refined isotropically. Disordered THF
molecules (2, 3) were refined with distance restraints and
restraints for the anisotropic displacement parameters. CCDC-
244078 (2), CCDC-244079 (3), and CCDC-244080 (4) contain
the supplementary crystallographic data for this paper. These
data can be obtained free of charge via www.ccdc.
cam.ac.uk/conts/retrieving.html (or from the Cambridge Crys-
170.6 ppm (C N); 27Al NMR (78.2 MHz, C6D6, 258C, [Al(H2O)6]3+
)
d = 101 ppm. MS (70 eV): m/z (%): 728 (58) [M+], 663 (100) [M+(Cp].
Angew. Chem. Int. Ed. 2004, 43, 6192 –6196
www.angewandte.org
ꢀ 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6195

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ꢀ 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 6192 –6196