COMMUNICATIONS
Maehashi, K.-I. Maruya, K. Domen, K.-I. Aika, T. Onishi, Chem. Lett.
1984, 747.
tives of ZrO2. One EtMe4C5 ligand is sterically equivalent to
three OI positions, while the interstitial O coordinates to
zirconium from the center of the plane formed by the four OII
atoms by enlarging the OII-Zr-OII angles (av 74.18 in ZrO2).
The Zr (m3-O) bond lengths in 2 and 3 are between the Zr OI
(2.07 ) and Zr OII (2.21 ) bond lengths, while the Zr (m6-
O) bond lengths are comparable to those of Zr OII.
[2] a) J. Kondo, K. Domen, T. Onishi, Res. Chem. Intermed. 1993, 19, 521;
b) S.-C. Moon, K. Tsuji, T. Nomura, M. Anpo, Chem. Lett. 1994, 2241.
[3] a) T. Yamaguchi, H. Sasaki, K. Tanabe, Chem. Lett. 1973, 1017; b) S.-
C. Moon, M. Fujino, H. Yamashita, M. Anpo, J. Phys. Chem. B 1997,
101, 369; c) A. Satoh, H. Hattori, K. Tanabe, Chem. Lett. 1983, 497.
[4] K. Kaneda, Y. Kawanishi, S. Teranishi, Chem. Lett. 1984, 1481.
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[7] L. M. Babcock, V. W. Day, W. G. Klemperer, J. Chem. Soc. Chem.
Commun. 1988, 519.
In summary we describe a new method for the preparation
of organozirconium oxides by hydrolysis of an organozirco-
nium chloride at low temperatures. Using this method, we
have obtained the organozirconium oxides 2 and 3. In
comparison to the traditional preparation of ZrO2 from ZrCl4
at 10008C the new route yields crystalline products below
room temperature. The core structures of 2 and 3 can be
regarded as a dimer of the previously reported [{(Cp*ZrCl)(m-
OH)}3(m3-OH)(m3-O)] ´ 2THF cluster[7] (without containing
six HCl, four THF, and one H2O molecules). We assume that
the formation of 2 proceeds via zirconium hydroxide and
amide intermediates. KH and the two-phase system (NH3/
toluene) are important for the formation of 2. The more
symmetric coordinated mesitylene leads to the more sym-
metric molecule of 3, but has evidently no influence on the
core structure. Further studies using this new method for the
preparation of Ti O, Hf O, Al O, and rare-earth systems are
in progress.
[8] L. M. Babcock, V. W. Day, W. G. Klemperer, Inorg. Chem. 1989, 28,
806.
[9] G. Bai, H. W. Roesky, M. Noltemeyer, H. Hao, H.-G. Schmidt,
Organometallics 2000, 19, 2823.
Â
[10] G. Bai, P. Müller, H. W. Roesky, I. Uson, Organometallics 2000, 19,
4675.
[11] G. Bai, H. W. Roesky, H.-G. Schmidt, M. Noltemeyer, Organometal-
lics 2001, in press.
[12] a) M. Allbutt, G. W. A. Fowles, J. Inorg. Nucl. Chem. 1963, 25, 67;
b) G. W. A. Fowles, F. H. Pollard, J. Chem. Soc. 1953, 4128; c) G. W. A.
Fowles, F. H. Pollard, J. Chem. Soc. 1953, 2588.
[13] D. Nicholls, Inorganic Chemistry in Liquid Ammonia, Monograph 17,
Elsevier, New York 1979, p. 7.
[14] G. L. Hillhouse, J. E. Bercaw, J. Am. Chem. Soc. 1984, 106, 5472.
Â
Â
[15] R. Gomez-Sal, A. Martín, M. Mena, C. Yelamos, J. Chem. Soc. Chem.
Commun. 1995, 2185.
[16] a) Crystal data for 2: C73H110O9Zr6 (including one toluene molecule),
Å
Mr 1678.93, triclinic, space group P1, a 12.959(3), b 14.341(4),
c 19.189(5) , a 82.85(3), b 84.562(17), g 83.767(13)8, V
3
3505.7(15) 3, Z 2, 1calcd 1.591 Mgm
,
F(000) 1720, l
0.71073 , T 200(2) K, m(MoKa) 0.914 mm 1. Data for the struc-
ture were collected on a Stoe-Siemens-AED2 four-circle diffractom-
eter. Intensity measurement was performed at 200(2) K on a rapidly
cooled crystal with the dimensions 1.0 Â 0.6 Â 0.4 mm3 in an oil drop[25]
in the range 7.04 ꢀ 2q ꢀ 50.108. Of the 15669 measured reflections,
12318 were independent (Rint 0.0787). The structure was solved by
direct methods (SHELXS-90)[26] and refined with all data by full-
matrix least-squares on F 2.[27] The hydrogen atoms of C H bonds were
added in idealized positions. R1 0.0408 for I > 2s(I), wR2 0.1187
for all data. The final difference Fourier synthesis gave a min./max.
residual electron density 1.173/ 0.891 e 3. b) Crystal data for 3:
C75H114O9Zr6 (including one mesitylene molecule), Mr 1706.98,
monoclinic, space group C2/c, a 22.641(5), b 13.0808(11), c
Experimental Section
2: H2O (0.08 g, 4.5 mmol) was added to the solution of 1 (1.04 g, 3.0 mmol)
in toluene (80 mL) at room temperature. The solution turned light yellow
and was stirred for 2 h at this temperature. KH (0.37 g, 9.2 mmol) was
added to the solution, and then ammonia (50 mL) was condensed onto the
resulting suspension at 788C with stirring. The mixture was stirred for 1 h
at this temperature. Then the excess of ammonia was allowed to evaporate
from the reaction mixture over a period of 4 h. During this time the mixture
slowly warmed to room temperature. The resulting solution was filtered
and the remaining yellowish brown precipitate was extracted with warm
toluene (508C, 2 Â 20 mL). The combined light yellow solution was
concentrated (to 15 mL) in vacuo and kept at 08C for one week. Colorless
crystals of 2 (0.10 g) were obtained. After concentration (to 5 mL) of the
filtrate, the solution was kept at 208C for one week. An additional crop of
24.550(6) , b 93.196(12)8, V 7259(2) 3, Z 4, 1calcd
3
1.562 Mgm
,
F(000) 3504,
l 0.71073 ,
T 200(2) K,
m(MoKa) 0.884 mm 1. Data for the structure were collected on a
Stoe-Siemens-AED2 four-circle diffractometer. Intensity measure-
ment was performed at 200(2) K on a rapidly cooled crystal in an oil
drop[25] with the dimensions 0.6 Â 0.6 Â 0.4 mm3 in the range 7.06 ꢀ
2q ꢀ 50.048. Of the 7944 measured reflections, 6365 were independent
(Rint 0.0330). The structure was solved by direct methods (SHELXS-
90)[26] and refined with all data by full-matrix least-squares on F 2.[27]
The hydrogen atoms of C H bonds were added in idealized positions.
R1 0.0307 for I > 2s(I), wR2 0.0683 for all data. The final differ-
2 (0.11 g) was obtained. Total yield 0.21 g (25%); m.p. > 4108C; IR (Nujol):
1
nÄ 1580, 1309, 1261, 1097, 1050, 1023, 779, 727, 659, 562, 506, 454 cm
;
1H NMR (200 MHz, C6D6, 608C): d 2.74 (q, J 7.5 Hz, 12H; CH2Me),
3
2.23, 2.17 (s, 72H; C5Me4), 1.08 (t, 3J 7.5 Hz, 18H; CH2Me); EI-MS: m/z
(%): 1586 (4) [M
C7H8], 1437 (100) [M
C7H8 EtMe4C5]; elemental
analysis (%) calcd for C73H110O9Zr6 (1679.0): C 52.2, H 6.6; found: C 52.7, H
6.7.
3: Crystals of 2 (0.05 g) were dissolved in warm mesitylene (808C; 8 mL).
The resulting colorless solution was kept at 08C for one week.
A
ence Fourier synthesis gave a min./max. residual electron density
quantitative yield of colorless crystals of 3 was obtained; m.p. > 4108C;
3
0.476/ 0.756 e
. Crystallographic data (excluding structure
EI-MS: m/z (%): 1586 (12) [M
C9H12], 1437 (100) [M
C9H12 Et-
factors) for the structures reported in this paper have been deposited
with the Cambridge Crystallographic Data Centre as supplementary
publication no. CCDC-155721 (2) and CCDC-155720 (3). Copies of
the data can be obtained free of charge on application to CCDC, 12
Union Road, Cambridge CB21EZ, UK (fax: (44)1223-336-033;
e-mail: deposit@ccdc.cam.ac.uk).
Me4C5].
Received: January 15, 2001 [Z16425]
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303.
[18] W. E. Hunter, D. C. Hrncir, R. Vann Bynum, R. A. Penttila, J. L.
Atwood, Organometallics 1983, 2, 750.
[19] G. Fachinetti, C. Floriani, A. Chiesi-Villa, C. Guastini, J. Am. Chem.
Soc. 1979, 101, 1767.
[20] R. P. Ziebarth, J. D. Corbett, J. Am. Chem. Soc. 1987, 109, 4844.
[21] J. D. Smith, J. D. Corbett, J. Am. Chem. Soc. 1985, 107, 5704.
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2158
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