R. Faissner, G. Huttner, E. Kaifer, P. Rutsch
FULL PAPER
tered, washed with diethyl ether (3 ϫ 10-mL portions), and dried
in vacuo.
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W. Hewertson, H. R. Watson, J. Chem. Soc. 1962, 84,
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1490Ϫ1494.
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569Ϫ592.
G. M. Whitesides, C. P. Casey, J. K. Krieger,
[1c]
[(6a-κ2P)NiCl2] (12a): Starting material: 6a. Recrystallisation from
CH2Cl2/diethyl ether afforded 12a (525 mg, 0.82 mmol, 82%) in the
form of red crystals suitable for X-ray structure analysis, m.p.
212 °C (decomposition). 31P NMR (CD2Cl2, Ϫ40 °C): δ ϭ 10.7
ppm (s).
[(6b-κ2P)NiCl2] (12b): Starting material: 6b. Recrystallisation from
CH2Cl2/diethyl ether afforded 12b (650 mg, 0.93 mmol, 93%) in the
form of red crystals suitable for X-ray structure analysis, m.p.
248 °C (decomposition). 31P NMR (CD2Cl2, Ϫ40 °C): δ ϭ 15.6
ppm (s).
M. J. Burk, J. E.
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H. Heidel, G. Huttner, G. Helmchen, Z. Naturforsch., Teil
[(11-κ2P)NiCl2] (12c): Starting material: 11. Removal of the solvent
afforded 12c (585 mg, 0.75 mmol, 75%) in the form of an orange,
B 1993, 48, 1681Ϫ1692.
H. Heidel, G. Huttner, R. Vogel,
[3b]
[3c]
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T. Seitz, A.
[3d]
1
microcrystalline solid. H NMR and 13C NMR: no sharp signals
Muth, G. Huttner, Chem. Ber. 1994, 127, 1837Ϫ1842.
H.
Heidel, G. Huttner, L. Zsolnai, Z. Naturforsch., Teil B 1995,
could be detected, due to a dynamic process. 31P NMR (CD2Cl2,
50, 729Ϫ734. [3e] G. Reinhard, R. Soltek, G. Huttner, A. Barth,
2
2
Ϫ40 °C): δ ϭ Ϫ4.5 ppm (d, JP,P ϭ 95 Hz, PMes2), 4.0 (d, JP,P
ϭ
[3f]
O. Walter, L. Zsolnai, Chem. Ber. 1996, 129, 97Ϫ108.
Antelmann, U. Winterhalter, G. Huttner, B. C. Janssen, J. Vo-
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1997, 130, 1279Ϫ1294.
halter, S. Cunskis, Eur. J. Inorg. Chem. 1998, 675Ϫ692.
Soltek, G. Huttner, Eur. J. Inorg. Chem. 1998, 1417Ϫ1424.
B.
95 Hz, PPh2).
[3g]
For crystallographic data of 12a and 12b, see Table 3; for further
analytical data of 12aϪ12c, see Tables 5Ϫ7.
[3h]
A. Jacobi, G. Huttner, U. Winter-
[(8-κ2N,P)PdCl2] (13): A solution of ligand 8 (210 mg, 0.5 mmol)
in ethanol (15 mL) was added rapidly to a suspension of (η4-
cod)PdCl2 (145 mg, 0.5 mmol) in ethanol (10 mL). Within a few
minutes the yellow reaction mixture became clear. After the mix-
ture had been stirred at 25 °C for 12 h, all volatiles were removed
in vacuo. The residual yellow solid was washed with diethyl ether
(3 ϫ 10-mL portions) and dried in vacuo. Recrystallisation from
CH2Cl2/diethyl ether afforded 13 (180 mg, 0.33 mmol, 66%) in the
form of yellow crystals suitable for X-ray structure analysis. FT-IR
(CH2Cl2): ν˜ ϭ 1732 cmϪ1 vs (CO), 1438 m (PPh). 31P NMR
(CD2Cl2): δ ϭ 19.6 ppm (s). For crystallographic data, see Table 3;
for further analytical data, see Tables 4, 6 and 7.
[3i]
R.
[3j]
R. Soltek, G. Huttner, L. Zsolnai, A. Driess, Inorg. Chim. Acta
1998, 269, 143Ϫ156.
[3k]
J. Vogelgesang, G. Huttner, E. Kaifer,
P. Kircher, P. Rutsch, S. Cunskis, Eur. J. Inorg. Chem. 1999,
2187Ϫ2199.
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L. Zsolnai, Chem. Ber. 1994, 127, 501Ϫ506.
[(8-κ2N,P)(η4-nbd)Rh]PF6 (14·PF6): [(η4-nbd)RhCl]2 (230 mg,
0.5 mmol) was dissolved in acetone (5 mL). In a second flask, po-
tassium hexafluorophosphate (195 mg, 1.05 mmol) was dissolved
in acetone (5 mL, 0.1 mL of water added). This solution was added
to the orange rhodium() solution. A colourless KCl precipitate
formed over 5 min, while the colour of the reaction mixture faded.
A solution of ligand 8 (370 mg, 1.0 mmol) in CH2Cl2 (5 mL) was
then added. After the mixture had been stirred at 25 °C for 1 h, all
volatiles were removed in vacuo. The residue was taken up in ace-
tone (20 mL) and dried with MgSO4. The insoluble KCl was re-
moved by filtering the solution through Kieselguhr. Removal of the
solvent in vacuo and recrystallisation from CH2Cl2/diethyl ether
afforded 14·PF6 (640 mg, 0.9 mmol, 90%) in the form of orange
crystals suitable for X-ray structure analysis, m.p. 203 °C (de-
composition). FT-IR (CH2Cl2): ν˜ ϭ 1725 cmϪ1 vs (CO), 1437 m
(PPh). 31P NMR (CD2Cl2): δ ϭ Ϫ144.2 ppm (sept, 1JP,F ϭ 711 Hz,
[6]
[6a] T. Seitz, A. Muth, G. Huttner, T. Klein, O. Walter, M. Fritz,
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L. Zsolnai, J. Organomet. Chem. 1994, 469, 155Ϫ162.
Seitz, A. Muth, G. Huttner, Z. Naturforsch., Teil B 1995, 50,
1045Ϫ1049.
Zsolnai, Z. Naturforsch., Teil B 1995, 50, 1287Ϫ1306.
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T. Seitz, A. Asam, G. Huttner, O. Walter, L.
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[6e]
1998, 553, 433Ϫ441.
P. Schober, R. Soltek, G. Huttner, L.
[6f]
Zsolnai, K. Heinze, Eur. J. Inorg. Chem. 1998, 1407Ϫ1415.
J. Vogelgesang, A. Frick, G. Huttner, P. Kircher, Eur. J. Inorg.
Chem. 2001, 949Ϫ971.
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A. Muth, A. Asam, G. Huttner, A. Barth, L. Zsolnai,
[7b]
Chem. Ber. 1994, 127, 305Ϫ311.
G. Huttner, A. Asam, O. Walter, M. Büchner, L. Zsolnai,
Chem. Ber. 1995, 128, 63Ϫ70.
B. C. Janssen, V. Sernau,
[7c]
P. Schober, G. Huttner, L.
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1971, 5, 1717Ϫ1723.
[8]
[9]
1
PF6؊), 29.8 (d, JRh,P ϭ 174 Hz, PPh2). For crystallographic data,
D. A. Blinn, R. S. Button, V. Farazi, M. K. Neeb, C. L. Tapley,
T. E. Trehearne, S. D. West, T. L. Kruger, B. N. Storhoff, J.
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see Table 3; for further analytical data, see Tables 4, 6 and 7.
[10] [10a]
[10b]
Acknowledgments
H. Wurziger, Kontakte (Darmstadt) 1988, 2, 36Ϫ41.
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We are indebted to the Deutsche Forschungsgemeinschaft and the
Fonds der Chemischen Industrie for financial support. One of us
(R. F.) is indebted to the local Graduiertenkolleg ‘‘Selektivität in
der organischen und metallorganischen Synthese und Katalyse’’ for
a scholarship. The technical support by T. Jannack (mass spectro-
metry) and the Microanalytical Laboratory of the Institute of Or-
ganic Chemistry is gratefully acknowledged. We are indebted to Dr.
J. Scherer and Dr. K. Heinze for their advice and help in solving the
crystal structure of 14·PF6.
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S. Cacchi, P. G. Ciattini, E. Morera, G. Ortar, Tetrahedron
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Lett. 1988, 29, 3117Ϫ3120.
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[13]
1692
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2003, 1681Ϫ1693