U. Siemeling, B. Neumann, H.-G. Stammler, O. Kuhnert
18, 1116; b) D. W. Stephan, F. GueÂrin, R. E. v. H. Sp-
ence, L. Koch, X. Gao, S. J. Brown, J. W. Swabey,
Q. Wang, W. Xu, P. Zoricak, D. G. Harrison, Organome-
tallics 1999, 18, 2046.
Experimental
All manipulations were performed in an inert atmosphere
(purified argon or dinitrogen) by using standard Schlenk and
cannula techniques or a conventional glovebox. Solvents and
reagents used were commercially available and were appro-
priately dried and purified by using standard procedures.
NMR spectra were recorded with a Bruker DRX 500 spec-
[3] U. Siemeling, A. Stammler, H.-G. Stammler, O. Kuh-
nert, Z. Anorg. Allg. Chem. 1999, 625, 845.
[4] a) S. Anfang, K. Harms, F. Weller, O. Borgmeier,
H. Lueken, H. Schilder, K. Dehnicke, Z. Anorg. Allg.
Chem. 1998, 624, 159; b) T. RuÈbenstahl, F. Weller,
S. Wocadlo, W. Massa, K. Dehnicke, Z. Anorg. Allg.
Chem. 1995, 621, 953.
[5] Reviews: a) U. Siemeling, Chem. Rev., in press;
b) H. ButenschoÈn, Chem. Rev., in press; c) J. Okuda,
T. Eberle, in: Metallocenes, Vol. 1 (eds.: A. Togni,
R. L. Halterman), Wiley-VCH, Weinheim, 1998, chap-
ter 7; d) P. Jutzi, T. Redeker, Eur. J. Inorg. Chem. 1998,
663; e) B. Wang, D. Deng, C. Qian, New J. Chem. 1995,
19, 515; f) P. Jutzi, U. Siemeling, J. Organomet. Chem.
1995, 500, 175; g) P. Jutzi, J. Dahlhaus, Coord. Chem.
Rev. 1994, 137, 179; h) J. Okuda, Comments Inorg.
Chem. 1994, 16, 185.
1
trometer operating at 500.13 MHz for H; external reference
1
(TMS: H, 13C, 29Si; 85% H3PO4: 31P). IR spectra were re-
corded with a Bruker Vector 22 FTIR spectrometer (KBr
windows, nujol mull). Mass spectra were obtained with a VG
Autospec instrument. Elemental analyses were performed by
the Microanalytical Laboratory of the UniversitaÈt Bielefeld.
[Fe{(C5H4)PPh2=NSiMe3]}2]: Our synthesis is a variation of
that published by Roesky et al. [6 a], avoiding, however, the
use of trimethylsilyl azide as solvent. Trimethylsilyl azide
(1.88 g, 16.4 mmol) was added to a solution of 1,1'-bis(diphe-
nylphosphanyl)ferrocene (3.63 g, 6.55 mmol) in toluene
(50 ml). The mixture was heated slowly and refluxed for 6 h.
Gas evolution started at ca. 90 °C. The solution was allowed
to cool to room temperature and filtered. The filtrate was
evaporated to dryness. The residue was recrystallised from
diethylether affording the product as a yellow solid. Yield
4.11 g (82%). Elemental analysis: C40H46N2FeP2Si2 (728.79);
C, 65.93 (calc. 65.92); H, 6.38 (6.36); N, 3.77 (3.84)%.
[6] a) H. W. Roesky, K. Swerat, F. Edelmann, Z. Natur-
forsch. 1988, 43 b, 231; b) K. V. Katti, U. Seseke,
H. W. Roesky, Inorg. Chem. 1987, 26, 814; c) K. V. Katti,
H. W. Roesky, M. Rietzel, Z. Anorg. Allg. Chem. 1987,
553, 123.
[7] F. Weller, D. NuûhaÈr, K. Dehnicke, Z. Anorg. Allg.
Chem. 1992, 615, 7.
1H-NMR (CDCl3, 25 °C): d = ±0.02 (s, 18 H, SiMe3), 4.05 (m, 4 H, C5H4),
4,47 (m, 4 H, C5H4), 7.29±7.32 (m, 8 H, Ph), 7.36±7.38 (m, 4 H, Ph), 7.44±
7.48 (m, 8 H, Ph); 13C{1H}-NMR (CDCl3, 25 °C): d = 4.10 (SiMe3), 73.1
(C5H4, d, |JPC| 13 Hz), 73.8 (C5H4, d, |JPC| 10 Hz), 77.8 (quart. C5H4),
127.8 (Ph, d, |JPC| 12 Hz), 130.4 (Ph), 131.2 (Ph, d, |JPC| 10 Hz), 136.7 (Ph,
d, |JPC| 104 Hz); 31P{1H}-NMR (CDCl3, 25 °C): d = ±1.51; 29Si{1H}-NMR
(CDCl3, 25 °C): d = ±12.9 (d, |JPSi| 24 Hz); EI-MS (70 eV): m/z = 728 (M+,
100%), 713 (M+±CH3, 67%).
[8] Crystallographic data: orange crystal (0.5 ´ 0.5 ´ 0.1 mm);
temperature 173(2) K; orthorhombic space group Pbca;
Z = 8; a = 1144.0(5), b = 1842.1(8), c = 3139.4(12) pm;
3
V = 6616(5) A ; qcalcd = 1.569 g/cm3; graphite-monochro-
Ê
Ê
mated MoKa radiation (k = 0.71073 A); Siemens P21
four-circle diffractometer; 2 hmax = 54.00°; reflections
collected/unique 7221/7221; semi-empirical absorption
correction from w scans; l(MoKa) = 1.151 mm±1; full-
matrix least-squares refinement on F2 (anisotropically
for all non-hydrogen atoms, H atoms in calculated posi-
tions using a riding model); data/restraints/parameters
7221/0/388; programmes used Siemens SHELXTL
PLUS and SHELXL 97; RF = 0.0736 for 3860 reflec-
tions with I > 2r(I), wRF2 = 0.1608 (all data). Crystallo-
graphic data for the structure have been deposited with
the Cambridge Crystallographic Data Centre. Copies of
the data can be obtained free of charge on application
to The Director, CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK (fax: int.code +(12 23)3 36-0 33; e-mail:
teched@chemcrys.cam.ac.uk).
[NbCl3{[NPPh2(C5H4)]2Fe}]: Acetonitrile (30 ml) was added
to niobium pentachloride (0.19 g, 0.71 mmol) and
[Fe{(C5H4)PPh2=NSiMe3}2] (0.52 g, 0.71 mmol). The mixture
was stirred at room temperature for 15 min. The orange so-
lution was kept at 40 °C for 24 h without stirring, affording
the product as orange crystals. Yield 0.27 g (49%). Elemen-
tal analysis: C34H28N2Cl3FeNbP2 (781.67); C, 51.43 (calc.
52.24); H, 4.14 (3.61); N, 3.86 (3.58)%.
1H-NMR (CDCl3, 25 °C): d = 4.32 (s, 4 H, C5H4), 5.02 (s, 4 H, C5H4), 7.57
(m, 8 H, Ph), 7.64±7.66 (m, 4 H, Ph), 7.82±7.86 (m, 8 H, Ph); 31P{1H}-
NMR (CDCl3, 25 °C): d = 18.4 (br.).
We are indebted to the Deutsche Forschungsgemeinschaft
for generous financial support. U. S. thanks Prof. Dr. Max
Herberhold for helpful discussions.
[9] a) W. W. Schoeller, U. Siemeling, O. Kuhnert, unpub-
lished results; b) A. Diefenbach, F. M. Bickelhaupt, Z.
Anorg. Allg. Chem. 1999, 625, 892.
[10] a) J. Sundermeyer, J. Putterlik, M. Foth, J. S. Field,
N. Ramesar, Chem. Ber. 1994, 127, 1201; b) K. A. Jùr-
gensen, Inorg. Chem. 1993, 32, 1521.
[1] Reviews: a) K. Dehnicke, M. Krieger, W. Massa, Coord.
Chem. Rev. 1999, 182, 19; b) K. Dehnicke, J. StraÈhle,
Polyhedron 1989, 8, 707.
[2] a) D. W. Stephan, J. C. Stewart, F. GueÂrin, R. E. v. H.
Spence, W. Xu, D. G. Harrison, Organometallics 1999,
826
Z. Anorg. Allg. Chem. 2000, 626, 825±826