Unique formation of a pentanuclear lanthanum(III) thiolate oxide cluster via control of hydrolysis

Article abstract of DOI:10.1021/ic052073v

The reaction of [(TMS)₂N]₃La(μ-Cl)Li(THF) ₃ (1) and HSPh produced a bimetallic-complex [{(TMS) ₂N}₂La(THF)]₂(μ-SPh)(μ-Cl)] (2). Compound [{(TMS)₂N}₂La₅O(SPh)₁₀LiCl ₂(THF)₆] (3) was prepared by control of the hydrolysis of 2 and LiCl or 1 and HSPh with the proper amount of water. 1 was treated first with 1/6 equiv of H₂O and then with equimolar HSPh; a polymeric complex [{(TMS)₂N}₂(μ-SPh)La(μ-SPh)Li(THF) ₂]_∞ (4) was isolated. 3 contains a central [(μ-SPh)₄(μ₃-SPh)₂{La(THF)} ₄(μ₃-O)]⁴⁺ tetrahedral fragment in which two La atoms are linked by a pair of μ-SPh^- and μ₃- Cl^- ligands to a [{(TMS)₂N}₂La]⁺ fragment, while the other two are bridged by two μ-SPh^- ligands to a [Li(THF)₂]⁺ fragment, forming a bee-shaped structure.

Full text of DOI:10.1021/ic052073v

Inorg. Chem. 2006, 45, 1885−1887
Unique Formation of a Pentanuclear Lanthanum(III) Thiolate Oxide
Cluster via Control of Hydrolysis
Hong-Xi Li,† Mei-Ling Cheng,† Zhi-Gang Ren,† Wen-Hua Zhang,† Jian-Ping Lang,*,†,‡ and Qi Shen†
Key Laboratory of Organic Synthesis of Jiangsu ProVince, School of Chemistry and Chemical
Engineering, Suzhou UniVersity, Suzhou 215123, Jiangsu, China, and State Key Laboratory of
Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, Shanghai 200032, People’s Republic of China
Received December 3, 2005
The reaction of [(TMS)2N]3La(
a bimetallic complex [ (TMS)2N
Compound [ (TMS)2N 2La5O(SPh)10LiCl2(THF)6] (3) was prepared
µ
-Cl)Li(THF)3 (1) and HSPh produced
oxygen-containing reagents such as O2,5 SeO2,6 and alkox-
ides7 were reported to be the oxygen sources in some cases.
Because the adventitious water in many reactions could not
be avoided, deliberate initialization of hydrolysis in these
reactions via the addition of a quantitative amount of water
was considered to be a useful way of obtaining organolan-
thanide-oxo derivatives. In this regard, several groups have
reported some interesting examples that are mainly related
to organolanthanide oxides supported by cyclopentadienyl,
alkoxide, amine, Schiff base, and carborane ligands.8 How-
ever, few attempts have been made on oxolanthanide
chalcogenolate complexes.9
{
}
2La(THF)]2( -SPh)( -Cl)] (2).
µ
µ
{
}
by control of the hydrolysis of 2 and LiCl or 1 and HSPh with the
1
proper amount of water. 1 was treated first with
/ equiv of H2O
6
and then with equimolar HSPh; a polymeric complex [
-SPh)La( -SPh)Li(THF)2]∞ (4) was isolated. 3 contains a central
-SPh)4(
which two La atoms are linked by a pair of
ligands to a [ (TMS)2N
2La]+ fragment, while the other two are
bridged by two
-SPh- ligands to a [Li(THF)2]+ fragment, forming
a bee-shaped structure.
{(TMS)2N} -
2
(
[(
µ
µ
µ
+
µ
3-SPh)2
{La(THF)
}
(
4 µ3-O)]4 tetrahedral fragment in
µ
-SPh- and 3-Cl-
µ
{
}
µ
On the other hand, we have recently been involved in the
preparation and determination of the structures and catalytic
properties of new aminolanthanide thiolate complexes.10 The
adventitious water was also observed to work in some of
our reactions, which made them quite messy. On the basis
of the considerations (i) that, in the presence of water, these
thiolate complexes tend to be hydrolyzed because of their
weak Ln-S bonds and the oxophilicity of the lanthanide-
(III) ion and (ii) that if such a hydrolysis is maintained to a
small scale, the resulting hydrolyzed species in solution may
interact with the remaining precursor to form new soluble
Organolanthanide compounds are usually prepared under
an inert gas using conventional Schlenk techniques with dried
solvents. However, some unexpected organolanthanide-oxo
complexes1 are incidentally isolated in varied yields even
when the reactions are carried out in a glovebox under an
inert gas where contamination by O2 and H2O is maintained
to be less than 1 ppm. Elucidation of the origin of the O
atom in these compounds proved difficult because of their
poor yield, solubility, or reproducibility. Therefore, the
introduction of the O atom in many cases is always ascribed
to the hydrolysis of lanthanide ions with the adventitious
water,2 even though cleavage of the C-O bond of tetrahy-
drofuran (THF) or ether,3 decomposition of grease,4 and
(3) (a) Evans, W. J.; Dominguez, R.; Hanusa, T. P. Organometallics 1986,
5, 1291-1296. (b) Aspinall, H. C.; Tillotson, M. R. Inorg. Chem.
1996, 35, 2163-2164. (c) Dube´, T.; Conoci, S.; Gambarotta, S.; Yap,
G. P. A. Organometallics 2000, 19, 1182-1185. (d) Deelman, B.-J.;
Booij, M.; Meetsma, A.; Teuben, J. H.; Kooijman, H.; Spekt, A. L.
Organometallics 1995, 14, 2306-2317.
* To whom correspondence should be addressed. E-mail:
jplang@suda.edu.cn.
(4) Kraut, S.; Magull, J.; Schaller, U.; Karl, M.; Harms, K.; Dehnicke,
K. Z. Anorg. Allg. Chem. 1998, 624, 1193-1201.
† Suzhou University.
(5) (a) Zhang, X.; Loppnow, G. R.; McDonald, R.; Takats, J. J. Am. Chem.
Soc. 1995, 117, 7828-7829. (b) Dube´, T.; Gambarotta, S.; Yap, G.
P. A. Organometallics 1998, 17, 3967-3973. (c) Geissinger, M.;
Magull, J. Z. Anorg. Allg. Chem. 1995, 621, 2043-2048. (d)
Moustiakimov, M.; Kritikos, M.; Westin, G. Inorg. Chem. 2005, 44,
1499-1504.
‡ Chinese Academy of Sciences.
(1) (a) Schumann, H.; Meese-Marktscheffel, J. A.; Esser, L. Chem. ReV.
1995, 95, 865-986. (b) Giljie, J. W.; Roesky, H. W. Chem. ReV. 1994,
94, 895-910. (c) Edelmann, F. T.; Freckmann, D. M. M.; Schumann,
H. Chem. ReV. 2002, 102, 1851-1896.
(2) (a) Schuetz, S. A.; Silvernail, C. M.; Incarvito, C. D.; Rheingold, A.
L.; Clark, J. L.; Day, V. W.; Belot, J. A. Inorg. Chem. 2004, 43, 6203-
6214. (b) Hitchcock, P. B.; Lappert, M. F.; Prashar, S. J. Organomet.
Chem. 1991, 413, 79-90. (c) Anwander, R.; Munck, F. C.; Priermeier,
T.; Scherer, W.; Runte, O.; Herrmann, W. A. Inorg. Chem. 1997, 36,
3545-3552. (d) Evans, W. J.; Boyle, T. J.; Ziller, J. W. J. Am. Chem.
Soc. 1993, 115, 5084-5092. (e) Guan, J.; Shen, Q.; Hu, J.; Lin, Y. J.
Struct. Chem. (China) 1990, 9, 184-187.
(6) Banerjee, S.; Huebner, L.; Romanelli, M. D.; Kumar, G. A.; Riman,
R. E.; Emge, T. J.; Brennan, J. G. J. Am. Chem. Soc. 2005, 127,
14008-14014.
(7) (a) Evans, W. J.; Sollberger, M. S.; Shreeve, J. L.; Olofson, J. M.;
Hain, J. H., Jr.; Ziller, J. W. Inorg. Chem. 1992, 31, 2492-2501. (b)
Yunlu, K.; Gradeff, P. S.; Edelstein, N.; Kot, W.; Shalimoff, G.; Streib,
W. E.; Vaartstra, B. A.; Caulton, K. G. Inorg. Chem. 1991, 30, 2317-
2321.
10.1021/ic052073v CCC: $33.50
Published on Web 02/01/2006
© 2006 American Chemical Society
Inorganic Chemistry, Vol. 45, No. 5, 2006 1885

COMMUNICATION
lanthanide thiolate and/or oxide complexes, we explored
some hydrolysis reactions of preformed organolanthanide
thiolate complexes with water. In this paper, we report an
interesting example where an unprecedented pentanulcear
lanthanum thiolate oxide complex was incidentally isolated
because of the adventitious water but was regenerated in an
acceptable yield via control of hydrolysis. This represents a
new route to oxolanthanide thiolate compounds and may be
applicable to other related systems.
of an amount of insoluble solids. Subsequent filtration fol-
lowed by a standard workup did produce 3 in 5% yield and
a thiolate-free compound [{(TMS)2N}3La] in 17% yield.12
A change of the 2/H2O molar ratios from 10:1 to 3:1 did
not increase the yield of 3. Interestingly, 3 could be obtained
in 19% yield from the direct addition of 1/10 equiv of water
to a mixture of 1 and equimolar HSPh.13 However, if a THF
1
solution of 1 was treated first with /6 equiv of water and
then with equimolar HSPh, only a polymeric complex
[{(TMS)2N}2(µ-SPh)La(µ-SPh)Li(THF)2]∞ (4) was isolated
in 22% yield.14 When the molar ratio of 1/H2O/HSPh was
changed to 1:0.1:1, a similar reaction afforded a mixture of
4 (15% yield) and 3 (0.5% yield). Therefore, these results
revealed that control of the proper amount of water in
hydrolysis and even the addition sequence between water
and other reagents are critical to the formation of 3. Com-
plexes 2-4 were sensitive to air and moisture and readily
soluble in THF and toluene, and their identities were con-
We previously reported the preparation of lanthanide thio-
late complexes from protonolysis of some preformed lantha-
nide(III) bis(trimethylsilyl)amino chloride complexes with
HSPh.10 When we ran an analogous reaction of [(TMS)2N]3La-
(µ-Cl)Li(THF)3 (1) (TMS ) trimethylsilyl) in THF with equi-
molar HSPh in n-hexane at ambient temperature, colorless
plates of the binuclear complex [{((TMS)2N)2La(THF)}2(µ-
SPh)(µ-Cl)]‚C7H8 (2‚C7H8)11 in 56% yield coupled with
several colorless prisms of a pentanuclear lanthanum thiolate
oxide cluster [{(TMS)2N}2La5O(SPh)10LiCl2(THF)6]‚C7H8
(3‚C7H8) were isolated. Where did the O atom in 3 originate?
When we bubbled dry O2 into a THF solution of 2 and equi-
molar LiCl for 1-30 min, it always resulted in an insoluble
white material, which ruled out the role of the adventitious
O2 in the formation of 3. Then we assumed that it might be
1
firmed by elemental analysis, H NMR, IR, and X-ray
analysis.
An X-ray analysis15a revealed that 2 contains two {((TMS)2-
N)2La(THF)}+ fragments that are interconnected by one
µ-Cl- and one µ-SPh-, forming a dimeric structure with a
crystallographic C2 axis running along the Cl1‚‚‚S1‚‚‚C13‚
‚‚C16 line (Figure 1). La1 and La1A adopt a distorted square-
pyramidal geometry, coordinated by one µ-Cl, one µ-S (SPh),
one O (THF), and two N {(TMS)2N} atoms.
1
the water that worked in this reaction. The addition of /6
equiv of water to a THF solution of 2 and equimolar LiCl
initiated an evident hydrolysis, which led to the formation
Compound 3 consists of a central [(µ-SPh)4(µ3-SPh)2{La-
(THF)}4(µ4-O)]4+ tetrahedral fragment in which La1 and
La1A are bridged by a pair of µ-SPh- ligands to a [Li-
(THF)2]+ fragment while La2 and La2A are connected by
two pairs of µ3-Cl- and µ-SPh- ligands to a [{(TMS)2N}2La]+
(8) (a) Bradley, D. C. Chem. ReV. 1989, 89, 1317-1322. (b) Mehrotra,
R. C.; Singh, A.; Tripathi, U. M. Chem. ReV. 1991, 91, 1287-1303.
(c) Zhou, X.; Ma, H.; Wu, Z.; You, X.; Xu, Z.; Huang, X. J.
Organomet. Chem. 1995, 503, 11-13. (d) Mehrotra, R. C.; Singh, A.
Chem. Soc. ReV. 1996, 1-13. (e) Wang, R.; Zheng, Z.; Jin, T.; Staples,
R. J. Angew. Chem., Int. Ed. 1999, 38, 1813-1815. (f) Liu, J.; Meyers,
E. A.; Shore, S. G. Inorg. Chem. 1998, 37, 5410-5411. (g) Bu¨rgstein,
M. R.; Roesky, P. W. Angew. Chem., Int. Ed. 2000, 39, 3549-551.
(h) Evans, W. J.; Greci, M. A.; Ziller, J. W. Inorg. Chem. 2000, 39,
3213-3220. (i) Daniele, S.; Hubert-Pfalzgraf, L. G.; Hitchcock, P.
B.; Lappert, M. F. Inorg. Chem. Commun. 2000, 3, 218-220. (j)
Evans, W. J.; Allen, N. T.; Greci, M. A.; Ziller, J. W. Organometallics
2001, 20, 2936-2937. (k) Westin, G.; Moustiakimov, M.; Kritikos,
M. Inorg. Chem. 2002, 41, 3249-3258. (l) Tasiopoulos, A. J.; O’Brien,
T. A.; Abboud, K. A.; Christou, G. Angew. Chem., Int. Ed. 2004, 43,
345-349. (m) Hosmane, N. S.; Maguire, J. A. Organometallics 2005,
24, 1356-1389. (n) Natrajan, L.; Pe´caut, J.; Mazzanti, M.; LeBrun,
C. Inorg. Chem. 2005, 44, 4756-4765. (o) Schuetz, S. A.; Day, V.
W.; Clark, J. L.; Belot, J. A. Inorg. Chem. Commun. 2002, 5, 706-
710. (p) Xu, G.; Wang, Z. M.; He, Z.; Lu, Z.; Liao, C. S.; Yan, C. H.
Inorg. Chem. 2002, 41, 6802-6807. (q) Roesky, P. W.; Canseco-
Melchor, G.; Zulys, A. Chem. Commun. 2004, 738-739.
(12) To a THF (30 mL) solution of 2 (0.926 g, 0.766 mmol) and anhydrous
LiCl (0.033 g, 0.766 mol) was slowly added a THF solution (2 mL)
of H2O (2.29 µL, 0.127 mmol). An amount of white precipitate was
observed to form quickly. The resulting mixture was stirred overnight
at room temperature and was concentrated to dryness in vacuo, leaving
a colorless oily residue. Hexane (10 mL) was added to the residue,
which was then stirred for another 15 min. After removal of the hexane
by vacuum evaporation, a dry free-flowing powder was left. The white
solid was washed thoroughly with hexane (4 × 5 mL). The resulting
solid was extracted with hot hexane (15 mL) and toluene (10 mL)
(about 35 °C). The combined extract was concentrated to ca. 10 mL
and cooled to 2 °C for several days to form colorless prisms of 3‚
C7H8, which were isolated by filtration, washed with hexane, and dried
in vacuo. Yield: 0.040 g (5%). Anal. Calcd for C96H134Cl2La5-
LiN2O7S10Si4: C, 43.78; H, 5.13; N, 1.06. Found: C, 43.41; H, 5.58;
N, 1.65. Mp: 136-138 °C. 1H NMR (400 MHz, THF-d8): δ 0.35 (s,
36H, Si(CH3)3), 1.73 (br, THF), 3.59 (br, THF), 6.81-7.73 (m, 50H,
Ph). IR (KBr disk): 3051 (w), 3001 (w), 2887 (w), 1598 (s), 1477
(s), 1441 (s), 1285 (s), 1252 (m), 1161 (m), 1068 (m), 1031 (s), 851
(s), 743 (s), 701 (m), 588 (m), 480 (w), 420 (s) cm-1. The solution
collected from hexane washing was concentrated to about 10 mL.
Compound [{(TMS)2N}3La] (5) was formed by cooling the solution
to -18 °C for several days. Yield: 0.16 g (17%). Anal. Calcd for
C18H54LaN3Si6: C, 34.87; H, 8.78; N, 6.78. Found: C, 34.53; H, 8.43;
N, 7.07. 1H NMR (400 MHz, THF-d8): δ 0.37 (s, Si(CH3)3). IR (KBr
disk): 2959 (s), 1466 (s), 1370 (w), 1355 (m), 1261 (m), 1175 (m),
(9) Pernin, C. G.; Ibers, J. A. Inorg. Chem. 1997, 36, 3802-3803.
(10) (a) Li, H. X.; Ren, Z. G.; Zhang, Y.; Zhang, W. H.; Lang, J. P.; Shen,
Q. J. Am. Chem. Soc. 2005, 127, 1122-1123. (b) Li, H. X.; Zhang,
Y.; Ren, Z. G.; Cheng, M. L.; Wang, J.; Lang, J. P. Chin. J. Chem.
2005, 23, 1499-1502.
(11) To a THF (30 mL) solution of 1 (1.13 g, 1.28 mmol) was slowly
added a hexane (10 mL) solution of HSPh (0.131 mL, 1.28 mmol; d
) 1.073 g/mL, 99%). The clear colorless solution was stirred overnight
at ambient temperature and then was concentrated to dryness in vacuo.
The residue was extracted with toluene (10 mL × 2), and the solution
was combined and concentrated to ca. 10 mL. The solution was cooled
to -18 °C for several days to form colorless plates of 2‚C7H8, which
were isolated by filtration, washed with hexane, and dried in vacuo.
Yield: 0.43 g (56%). Anal. Calcd for C38H93ClLa2N4O2SSi8: C, 37.78;
H, 7.76; N, 4.64. Found: C, 37.26; H, 7.81; N, 4.33. Mp: 111-114
°C. 1H NMR (400 MHz, THF-d8): δ 0.54 (s, 72H, Si(CH3)3), 1.74
(br, THF), 3.61 (br, THF), 7.01-7.45 (m, 5H, Ph). IR (KBr disk):
3047 (w), 2955 (w), 2883 (w), 1576 (s), 1472 (s), 1433 (s), 1249 (s),
1085 (s), 1066 (m), 1023 (s), 842 (s), 738 (s), 694 (s), 576 (w), 418
1054 (s), 951 (s), 705 (w), 618 (w), 406 (w) cm-1
.
(13) To a THF (30 mL) solution of 1 (1.287 g, 1.46 mmol) was slowly
added a hexane (5 mL) solution of HSPh (0.150 mL, 1.46 mmol).
The solution was stirred overnight and then treated with a THF solution
(2 mL) of H2O (2.63 µL, 0.146 mmol). The clear colorless solution
went opaque and gradually developed some white precipitate. The
resulting mixture was again stirred overnight at room temperature. A
workup similar to that used in method 1 gave rise to colorless crystals
of 3‚C7H8. Yield: 0.14 g (19%).
(s) cm-1
.
1886 Inorganic Chemistry, Vol. 45, No. 5, 2006

COMMUNICATION
La1/La1A, La2/La2A, and La3 display a distorted square-
capped trigonal-prismatic coordination geometry, a distorted
bisquare-capped trigonal-prismatic coordination geometry,
and a distorted octahedral coordination geometry, respec-
tively (see the Supporting Information). The tetrahedral
coordination sphere of Li1 is completed by two µ-S and two
O atoms from THF molecules.
The structure of 4,15c similar to that of its praseodymium
analogue,10 contains a 1D wavelike chain structure in which
the two [{(TMS)2N}2La]+ and [Li(THF)2]+ fragments are
alternatively bridged by µ-SPh- ligands along the crystal-
lographic a axis (see the Supporting Information).
Figure 1. Molecular structure of 2 with 30% probability. All H atoms
are omitted for clarity.
Compounds 2-4 were found to initiate the polymerization
of ꢀ-caprolactone at ambient temperature in a few minutes
to give poly(ꢀ-caprolactone) with low polydispersity (Mw/
Mn ) 1.42-1.63). Compared with 1 and their mono- or
disubstituted (silylamino)lanthanide complexes,16 2-4 initi-
ated faster polymerization and produced poly(ꢀ-caprolactone)
with narrower molecular weight distribution. This result may
be ascribed to the weak Ln-S bonds in 2-4.17 The catalytic
activities in the polymerization of ꢀ-caprolactone decreased
in the order of 3 > 2 > 4 (see the Supporting Information)
mainly because of the different clusterings.
Figure 2. Molecular structure of 3 with 30% probability. All C and H
atoms are omitted for clarity.
In summary, the present work demonstrated that a unique
pentanuclear lanthanum benzenethiolate oxide compound 3,
once incidentally isolated, could be reproduced via control
of the hydrolysis of 2 and LiCl or 1 and HSPh with the
proper amount of water. This synthetic strategy may be
applied to the preparation of other new oxolanthanide thiolate
complexes with better catalytic performances. Studies in this
respect are ongoing in our laboratory.
fragment, thereby forming a bee-shaped structure (Figure
2).15b The whole molecule possesses a C2 axis running along
the La3‚‚‚O3‚‚‚Li1 line. The µ4-O atom lies at the center of
the La4 tetrahedron and interacts with four La atoms, with
La-O lengths ranging from 2.383(3) to 2.555(4) Å. The four
edges of the La4 tetrahedron are bridged by four µ-SPh-
ligands, while its two faces are capped with two µ3-SPh-
ligands. The mean Ln-S bond distance is 2.9766 Å. Each
La atom in this La4 tetrahedron is saturated by a THF
molecule, while La3 binds to two (TMS)2N- anions. Thus,
Acknowledgment. This work was supported by the
Distinguished Young Scholar Fund to J.-P.L. (Grant
20525101), the NSF of Jiangsu Province (Grant BK2004205),
the State Key Laboratory of Organometallic Chemistry of
SIOC (Grant 04-31), and the Key Laboratory of Organic
Synthesis of Jiangsu Province (JSK001) in China. The
authors also thank Y. Zhang for kind assistance in X-ray
analysis.
(14) To a THF (30 mL) solution of 1 (0.924 g, 1.07 mmol) was slowly
added a THF (2 mL) solution of H2O (3.22 µL, 0.179 mmol). Some
precipitate was observed to form within seconds. The mixture was
stirred overnight at room temperature and treated with a hexane (5
mL) solution of HSPh (0.110 mL, 1.07 mmol). After the resulting
mixture was stirred for one more night, the volatile species were
evaporated in vacuo, leaving an oily residue. Hexane (10 mL) was
added to the residue, which was stirred for another 15 min. After
removal of the hexane by vacuum evaporation, the solid was again
extracted with hot hexane (15 mL) and toluene (5 mL) (about 40 °C)
and filtered. Colorless crystals of 4 were formed by cooling the filtrate
to 2 °C for several days. Yield: 0.195 g (22%). Anal. Calcd for C32H62-
LiN2O2LaS2Si4: C, 46.35; H, 7.54; N, 3.38. Found: C, 46.53; H, 7.89;
N, 3.17. Mp: 145-147 °C. 1H NMR (400 MHz, THF-d8): δ 0.49 (s,
36H, Si(CH3)3), 1.71 (br, THF), 3.62 (br, THF), 6.99-7.61 (m, 10H,
Ph). IR (KBr, disk): 3058 (w), 2960 (m), 2880 (w), 1581 (s), 1450
(s), 1443 (m), 1256 (w), 1179 (m), 1090 (s), 1051 (m), 1027 (s), 890
Supporting Information Available: Crystallographic data for
2-4 (CIF) and synthesis and polymerization details (PDF). This
material is available free of charge via the Internet at http://
pubs.acs.org.
IC052073V
(16) (a) Evans, W. J.; Katsumata, H. Macromolecules 1994, 27, 2330-
2332. Agarwal, S.; Karl, M.; Anfang, S.; Dehnicke, K.; Greiner, A.
Polym. Prepr. (Am. Chem. Soc., DiV. Polym. Chem.) 1998, 39, 361-
362. (b) Hou, Z.; Wakatsuki, Y. Coord. Chem. ReV. 2002, 231, 1-22.
(c) Li, H. X.; Xu, Q. F.; Chen, J. X.; Cheng, M. L.; Zhang, Y.; Zhang,
W. H.; Lang, J. P.; Shen, Q. J. Organomet. Chem. 2004, 689, 3438-
3448.
(17) (a) Nakayama, Y.; Shibahara, T.; Fukumoto, H.; Nakamura, A.
Macromolecules 1996, 29, 8014-8016. (b) Hou, Z.; Zhang, Y.;
Tezuka, H.; Xie, P.; Tardif, O.; Koizumi, T.; Yamazaki, H.; Wakatsuki,
Y. J. Am. Chem. Soc. 2000, 122, 10533-10543. (c) Ma, H.; Spaniol,
T. P.; Okuda, J. Dalton Trans. 2003, 4770-4780. (d) Kim, J. Y.;
Livinghouse, T. Org. Lett. 2005, 7, 1737-1739. (e) Ma, H.; Okuda,
J. Macromolecules 2005, 38, 2665-2673.
(w), 743 (s), 696 (m), 660 (w), 481 (m), 416 (w) cm-1
.
(15) (a) Crystal data for 2: monoclinic, space group C2/c, a ) 20.7862-
(15) Å, b ) 11.4386(7) Å, c ) 30.107(2) Å, â ) 106.665(2)°, V )
6857.8(8) Å3, Z ) 4, Fcalcd ) 1.258 g/cm3, µ(Mo KR) ) 1.471 cm-1
,
R1 ) 0.0422, wR2 ) 0.0972, GOF ) 1.120. (b) Crystal data for 3:
monoclinic, space group C2/c, a ) 26.247(4) Å, b ) 20.784(2) Å, c
) 25.361(3) Å, â ) 114.473(3)°, V ) 12592(3) Å3, Z ) 4, Fcalcd
)
1.438 g/cm3, µ(Mo KR) ) 1.952 cm-1, R1 ) 0.0599, wR2 ) 0.1365,
GOF ) 1.114. (c) Crystal data for 4: triclinic, space group P1h, a )
8.718(3) Å, b ) 11.384(4) Å, c ) 22.573(8) Å, R ) 103.077(11)°, â
) 96.329(12)°, γ ) 90.864(7)°, V ) 2167.1(12) Å3, Z ) 2, Fcalcd
)
1.271 g/cm3, µ(Mo KR) ) 1.220 cm-1, R1 ) 0.0695, wR2 ) 0.1708,
GOF ) 1.037.
Inorganic Chemistry, Vol. 45, No. 5, 2006 1887