P-Halogeno(imino)methylenephosphoranes
FULL PAPER
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4
(d, JPC ϭ 65.3 Hz, PϭC), 122.7 (d, JPC ϭ 8.9 Hz, m-Ar), 140.8 SHELXTL-Plus[15], SHELXL-93[16]). Non-hydrogen atoms were
(d, 2JPC ϭ 23.3 Hz, ipso-Ar), 142.9 (d, 3JPC ϭ 15.7 Hz, o-Ar), 145.0
refined anisotropically; H atoms were refined using a riding model;
5
(d, JPC ϭ 10.7 Hz, p-Ar). Ϫ MS (70 eV); m/z (%): 483 (11) [Mϩ], the tert-butyl groups were found to be disordered. Full details of
290 (100) [tBu3C6H2NPϩ]. Ϫ C25H47ClNPSi2 (484.2): calcd. C
the crystal structure determinations (except structure factors) have
been deposited with the Cambridge Crystallographic Data Centre
as supplementary publication no. CCDC-100474 (2, 3, 4). Copies
may be obtained free of charge on application to CCDC, 12 Union
Road, Cambridge CB2 1EZ, U.K. [Fax: (internat.) ϩ 44(0)1223/
336033; E-mail: deposit@ccdc.cam.ac.uk].
62.01, H 9.78; found C 62.22, H 9.84.
Bromo[(2,4,6-tri-tert-butylphenyl)imino][bis(trimethylsilyl)-
methylene]phosphorane (4): To a solution of 3 (1.21 g, 2.5 mmol)
in 10 ml of THF was added an equimolar amount of Me3SiBr and
the reaction mixture was stirred for 2 h at room temp. The solvent
and the halosilanes were then removed in vacuo and the residue
was crystallized from a small volume of n-hexane. The product was
obtained as an orange, crystalline solid. Ϫ Yield 1.16 g (87.5%),
m.p. 99Ϫ101°C. Ϫ 31P NMR (C6D6): δ ϭ 65.2. Ϫ 1H NMR
(C6D6): δ ϭ 0.40 (s, 9 H, SiMe3), 0.60 (s, 9 H, SiMe3), 1.45 (s, 9
[1] [1a]
E. Niecke, W. Flick, Angew. Chem. 1974, 86, 128; Angew.
Chem. Int. Ed. Engl. 1974, 13, 585. Ϫ [1b] O. J. Scherer, N. Kuhn,
Chem. Ber. 1974, 107, 2123. Ϫ
[1c]
S. Pohl, E. Niecke, B. Krebs,
Angew. Chem. 1975, 87, 284; Angew. Chem. Int. Ed. Engl. 1975,
14, 261.
[2]
H, p-tBu), 1.73 (s, 18 H, o-tBu), 7.62 (d, 5JPH ϭ 3.6 Hz, 2 H, C6H2).
Multiple Bonds and Low Coordination in Phosphorus Chemistry
(Eds.: M. Regitz, O. J. Scherer), Thieme, Stuttgart, 1990.
3
Ϫ
13C NMR (C6D6): δ ϭ 4.6 (s, SiMe3), 5.0 (d, JPC ϭ 5.7 Hz,
[3] [3a]
E. Niecke, D. Gudat in ref.[2], p. 392Ϫ404, and cited litera-
5
ture. Ϫ
R. Appel in ref.[2], p. 367Ϫ374, and cited literature.
SiMe3), 32.1 (d, JPC ϭ 6.1 Hz, p-CCH3), 32.5 (d, JPC ϭ 2.6 Hz,
o-CCH3), 35.2 (d, JPC ϭ 3.8 Hz, p-CCH3), 37.0 (d, JPC ϭ 3.8 Hz,
o-CCH3), 58.2 (d, JPC ϭ 50.6 Hz, PϭC), 122.8 (d, JPC ϭ 10.2
[3b]
4
[3c]
Ϫ
H. Heydt in ref.[2], p. 375Ϫ391.
[4]
[5]
[4a] R. Appel, T. Gaitzsch, F. Knoch, G. Lenz, Chem. Ber. 1996,
1
4
[4b]
119, 1977. Ϫ
E. Niecke, M. Frost, V. von der Gönna, A.
2
3
Hz, m-Ar), 142.0 (d, JPC ϭ 24.4 Hz, ipso-Ar), 143.2 (d, JPC
ϭ
Ruban, W. W. Schoeller, Angew. Chem. 1994, 106, 2170Ϫ2172;
Angew. Chem. Int. Ed. Engl. 1994, 33, 2111Ϫ2113.
17.1 Hz, o-Ar), 145.3 (d, 5JPC ϭ 12.2 Hz, p-Ar). Ϫ MS (70 eV); m/z
(%): 527 (52) [Mϩ], 290 (100) [tBu3C6H2NPϩ]. Ϫ C25H47BrNPSi2
(528.7): calcd. C 56.79, H 8.96; found C 56.98, H 9.04.
[5a] A. R. Barron, A. H. Cowley, J. Chem. Soc., Chem. Commun.
[5b]
1987, 1272. Ϫ
H. J. Metternich, E. Niecke, Angew. Chem.
1991, 103, 336Ϫ337; Angew. Chem. Int. Ed. Engl. 1991, 30,
[5c]
Crystal-Structure Analyses. Ϫ Crystal Data: 2: C25H47INPSi2,
Mr ϭ 575.7, red tablets, 0.60 ϫ 0.50 ϫ 0.35 mm; monoclinic, space
312Ϫ313. Ϫ
P. Becker, H. Brombach, G. David, M. Leuer,
H. J. Metternich, Chem. Ber. 1992, 125, 771Ϫ774.
G. Fink, V. Möhring, Stud. Surf. Sci. Catal. (Catal. Polym. Ole-
fins) 1986, 25, 231.
[6]
[7]
˚
group P21/c (No. 14), a ϭ 8.853(3), b ϭ 33.25(1), c ϭ 10.666(4) A,
β ϭ 99.75(3)°, V ϭ 3094(2) A , Z ϭ 4, Dx ϭ 1.24 Mg mϪ3, µ(Mo-
3
˚
B. Schinkels, A. Ruban, M. Nieger, E. Niecke, J. Chem. Soc.,
Chem. Commun. 1997, 293Ϫ294.
Kα) ϭ 1.18 mmϪ1, T ϭ 293(2) K, F(000) ϭ 1200, number of reflec-
K. Karaghiosoff in ref.[2], p. 463Ϫ471.
[8]
[9]
tions: 7843 (7145 independent, Rint ϭ 0.025), R(F) ϭ 0.054, wR(F2
S. Berger, S. Braun, H.-W. Kalinowski, NMR Spectroscopy of
Main Group Elements, vol. III, Thieme Verlag, Stuttgart, 1993.
E. Niecke, D.-A.Wildbredt, Chem. Ber. 1980, 113, 1549Ϫ1565.
A. Ruban, M. Nieger, E. Niecke, Angew. Chem. 1993, 105,
1544Ϫ1545; Angew. Chem. Int. Ed. Engl. 1993, 32, 1419Ϫ1420.
D. Gudat, E. Niecke, A. Ruban, V. von der Gönna, Mag. Res.
Chem. 1996, 34, 799Ϫ806.
all data)
ϭ 0.153 (266 parameters, 50 restraints). Ϫ 3:
[10]
[11]
C25H47ClNPSi2, Mr ϭ 484.2, yellow blocks, 0.40 ϫ 0.30 ϫ 0.20
mm, monoclinic, space group P21/c (No. 14), a ϭ 8.902(2), b ϭ
3
˚
˚
32.825(5), c ϭ 10.516(1) A, β ϭ 98.95(1)°, V ϭ 3035.4(9) A , Z ϭ
4, Dx ϭ 1.06 Mg mϪ3, µ(Cu-Kα) ϭ 2.44 mmϪ1, T ϭ 293(2) K,
F(000) ϭ 1056, number of reflections: 4845 (4442 independent,
Rint ϭ 0.096), R(F) ϭ 0.075, wR(F2 all data) ϭ 0.232 (266 param-
eters, 62 restraints). Ϫ 4: C25H47BrNPSi2, Mr ϭ 528.7, orange
blocks, 0.80 ϫ 0.70 ϫ 0.50 mm, monoclinic, space group P21/c
[12]
[13] [13a] E. Niecke, M. Nieger, F. Reichert, Angew. Chem. 1988, 100,
[13b]
1781; Angew. Chem. Int. Ed. Engl. 1988, 27, 1715. Ϫ
V.
Romanenko, L. S. Kachkovskaja, M. I. Povolotskii, A. N. Cher-
nega, M. Yu. Antipin, Yu. T. Struchkov, L. N. Markovskii, Zh.
[13c]
Obshch. Khim. 1988, 58, 958Ϫ969. Ϫ
M. Nieger, Thesis,
˚
[13d]
(No. 14), a ϭ 8.851(2), b ϭ 32.87(1), c ϭ 10.556(4) A, β ϭ
Universität Bonn, 1989. Ϫ
E. Niecke, D. Gudat, Angew.
99.15(3)°, V ϭ 3032(2) A , Z ϭ 4, Dx ϭ 1.16 Mg mϪ3, µ(Mo-Kα) ϭ
3
˚
Chem. 1991, 103, 251Ϫ270; Angew. Chem. Int. Ed. Engl. 1991,
30, 217Ϫ237.
1.50 mmϪ1, T ϭ 293(2) K, F(000) ϭ 1128, number of reflections:
5622 (5325 independent, Rint ϭ 0.053), R(F) ϭ 0.055, wR(F2 all
data) ϭ 0.151 (266 parameters, 62 restraints). An absorption cor-
rection on the basis of Ψ scans was applied.
[14] [14a] R. Appel, A. Westerhaus, Tetrahedron Lett. 1982, 23, 2017.
[14b]
Ϫ
R. Appel, K.-H. Dunken, E. Gaitzsch, T. Gaitzsch, Z.
Chem. 1984, 24, 384Ϫ385.
[15]
[16]
G. M. Sheldrick, SHELXTL-Plus, Siemens Analytical X-ray In-
struments Inc., Madison, Wisconsin, USA, 1989.
G. M. Sheldrick, SHELXL-93, University of Göttingen, 1993.
[97177]
Structure Solution and Refinement: The structures were solved by
direct methods and refined anisotropically on F2 (program system:
Eur. J. Inorg. Chem. 1998, 83Ϫ85
85