G. Bertrand, A. Baceiredo et al.
FULL PAPER
2
3
3
3
3
CHN), 2.64 (dq, JP, H 3.6 Hz, JH,H 7.1 Hz, 2H; PCH2), 1.32 (d, JH,H
(d, JP, H 6.6 Hz, 12H; CH3CH), 1.33 (d, JH,H 6.6 Hz, 12H; CH3CH),
1.18 (s, 3H; CH3CHSi), 1.15 ppm (s, 18H; CH3CHSi); 13C{1H} NMR
(C6D6): d 180.5 (d, 1JP, C 97.5 Hz, P C), 153.5 (d, 2JP, C 35.2 Hz, C N),
51.2 (d, 2JP, C 5.7 Hz, CHN), 47.2 (s, CHN), 46.0 (s, CHN), 41.4 (s, CH3N),
3
3
6.6 Hz, 6H; CH3CH), 1.22 (d, JH,H 7.1 Hz, 3H; CH3CP), 1.11 (d, JH,H
3
6.6 Hz, 6H; CH3CH), 1.07 (d, JH,H 6.6 Hz, 6H; CH3CH), 0.90 ppm (d,
3JH,H 6.6 Hz, 6H; CH3CH); 13C{1H} NMR (CDCl3): d 123.4 (d, JP, C
2
12.0 Hz, CN), 47.7 (d, 2JP, C 11.7 Hz, CHN), 47.1 (d, 2JP,C 11.2 Hz, CHN),
24.9(d, JP, C 6.5 Hz, CH3CHNP), 24.7 (d, 2JP, C 6.3 Hz, CH3CHNP), 19.6
2
24.7 (d, 2JP, C 6.6 Hz, CH3C), 24.5 (d, 2JP, C 6.7 Hz, CH3C), 24.4 (d, 2JP, C
(s, CH3CHN), 19.3 (s, CH3CHN), 18.5 (s, CH3CSi), 14.4 ppm (s, CHSi);
29Si{1H} NMR (C6D6): d À28.7 ppm.
2
1
6.4 Hz, CH3C), 22.6 (d, JP, C 16.9Hz, CH3CP), 16.1 ppm (d, JP, C
24.3 Hz, PCH); IR (pentane): nÄ 2232 cmÀ1 (CN); MS (EI): m/z: 285
Crystal structure determination for 4a and 9a: Crystal data for both
structures are presented in Table 1. All data were collected at low
temperatures by using an oil-coated shock-cooled crystal on a STOE-
IPDS diffractometer. The structures were solved by direct methods
(SHELXS-97)[21] and refined by using the least-squares method on F 2.[22]
All non-hydrogen atoms were refined anisotropically. The hydrogen atoms
of the molecules were geometrically idealized and refined using a riding
model. A numerical absorption correction was employed for structure 9a;
[M ]; elemental analysis calcd (%) for C15H32N3P: C 63.12, H 11.30, N
14.72; found: C 63.18, H 11.38, N 14.70
General procedure for the metalation silylation of phosphinonitriles 6'a,
6'b, 6c, and 6d: One equivalent of base (n-BuLi or LDA) was added to a
solution of the nitrile 6'a, 6'b, 6c, or 6d (1 mmol) in THF (10 mL) at
À788C. After the temperature increased to 08C, the solution mixture was
stirred at this temperature for 45 min. The mixture was then cooled again at
À788C, and one equivalent of R3SiCl (R Me or iPr) was added. After the
solution was slowly heated to room temperature (30 min), the solvent was
removed under vacuum, and the residue was extracted with pentane
(20 mL).
the min/max transmissions were 0.8338/0.9375. Two positions for
disordered cyclohexyl group in 9a were refined anisotropically by using
197 ADP and distance restraints.
a
CCDC-185685 and CCDC-185686 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of charge via
tallographic Data Centre, 12 Union road, Cambridge CB21EZ, UK; (fax:
(44)1223 336 033; or e-mail: deposit@ccdc.cam.ac.uk).
a-Phosphinonitrile 6e: Yellow oil (92% yield); 31P{1H} NMR (C6D6): d
1
3
3
47.4 ppm; H NMR (C6D6): d 3.57 (sept d, JH,H 6.6 Hz, JP, H 12.1 Hz,
2H; CHN), 3.38 (sept d, 3JH,H 6.6 Hz, 3JP, H 11.9Hz, 2H; CHN), 1.89(d,
2JP, H 2.5 Hz, 1H; PCH), 1.25 (d, JH,H 6.6 Hz, 6H; CH3CH), 1.14 (d,
3
3JH,H 6.6 Hz, 6H; CH3CH), 1.07 (d, 3JH,H 6.6 Hz, 6H; CH3CH), 0.99 (d,
3JH,H 6.6 Hz, 6H; CH3CH), 0.22 ppm (s, 9H; CH3Si); 13C{1H} NMR
2
2
(C6D6): d 121.1 (s, CN), 48.3 (d, JP,C 5.7 Hz, CHN), 48.0 (d, JP, C
2
2
7.0 Hz, CHN), 25.1 (d, JP, C 6.5 Hz, CH3C), 24.4 (d, JP, C 8.5 Hz,
2
2
Acknowledgements
CH3C), 24.1 (d, JP, C 8.8 Hz, CH3C), 24.0 (d, JP, C 9.1 Hz, CH3C), 21.3
1
3
(d, JP, C 56.6 Hz, PCH), À1.3 ppm (d, JP, C 6.3 Hz, CH3Si); IR (C6D6):
nÄ 2210 cmÀ1 (CN).
Thanks are due to the CNRS and UCR for financial support of this work.
Ketenimine 7d: Yellow oil (89% yield); 31P{1H} NMR (C6D6): d
61.4 ppm; 1H NMR (C6D6): d 3.57 (sept d, JH,H 6.6 Hz, JP, H
3
3
3
3
12.1 Hz, 2H; CHN), 3.38 (sept d, JH,H 6.6 Hz, JP, H 11.9Hz, 2H;
[1] a) A. Igau, H. Gr¸tzmacher, A. Baceiredo, G. Bertrand, J. Am. Chem.
Soc. 1988, 110, 6463; b) D. Bourissou, O. Guerret, F. P. Gabbai, G.
Bertrand, Chem. Rev. 2000, 100, 39 .
[2] G. Alcaraz, U. Wecker, A. Baceiredo, F. Dahan, G. Bertrand, Angew.
Chem. 1995, 107, 1358; Angew. Chem. Int. Ed. Engl. 1995, 34, 1246.
[3] a) V. Piquet, A. Baceiredo, H. Gornitzka, F. Dahan, G. Bertrand,
Chem. Eur. J. 1997, 3, 1757; b) V. Piquet, A. Baceiredo, F. Dahan, G.
Bertrand, C. R. Acad. Sci. Ser. IIc 1998, 123.
[4] a) F. Mathey, C. Charrier, N. Maigrot, A. Marinetti, L. Ricard, N. H.
Tran Huy, Comments Inorg. Chem. 1992, 13, 61; b) S. Kummer, U.
Zenneck, in Comprehensive Heterocyclic Chemistry II, Vol. 1b (Eds.:
A. R. Katritzky, C. W. Rees, E. F. Scriven), Pergamon, Oxford, 1996,
p. 1157.
[5] a) H. Gr¸tzmacher, H. Pritzkow, Chem. Ber. 1989, 122, 1417; b) N. V.
Lukashev, A. D. Averin, P. E. Zhichkin, M. A. Kazankova, I. P.
Beletskaya, Phosphorus, Sulfur Silicon Relat. Elem. 1996, 109 110,
609.
[6] G. Alcaraz, R. Reed, A. Baceiredo, G. Bertrand, J. Chem. Soc. Chem.
Commun. 1993, 1354.
[7] R. Reed, G. Bertrand, in Phosphorus-31NMR Spectral Properties in
Compound Characterisation and Structural Analysis (Eds.: L. D. Quin,
J. G. Verkade), VCH, New York, 1994, pp. 189 200.
[8] S. Goumri-Magnet, O. Polishchuk, H. Gornitzka, C. J. Marsden, A.
Baceiredo, G. Bertrand, Angew. Chem. 1999, 111, 3938; Angew. Chem.
Int. Ed. 1999, 38, 3727.
[9] a) T. S. Stevens, E. M. Creighton, A. B. Gordon, M. McNicol, J. Chem.
Soc. 1928, 3193; b) Advanced Organic Chemistry, 4th ed. (Ed.: J.
March), Wiley-Interscience, New York, 1992, pp. 1100 1102.
[10] A. Igau, A. Baceiredo, G. Trinquier, G. Bertrand, Angew. Chem. 1989,
101, 617; Angew. Chem. Int. Ed. Engl. 1989, 28, 621.
3
3
CHN), 1.89(d, JP,H 9.0 Hz, 3H; PCCH3), 1.21 (d, JH,H 6.6 Hz, 6H;
3
CH3CH), 1.19(d, JH,H 6.6 Hz, 6H; CH3CH), 1.06 (d, 3JH,H 6.6 Hz, 12H;
CH3CH), 0.38 ppm (s, 9H; CH3Si); 13C{1H} NMR (C6D6): d 185.2 (d,
2JP, C 9.4 Hz, P-C C), 48.1 (d, JP, C 8.1 Hz, CHN), 47.3 (d, JP, C
2
2
1
2
À
10.9Hz, CHN), 38.6 (d, JP, C 8.8 Hz, P C), 25.3 (d, JP, C 6.0 Hz,
2
2
CH3C), 24.9(d, JP,C 6.7 Hz, CH3C), 24.8 (d, JP, C 6.8 Hz, CH3C), 24.3
2
2
(d, JP, C 6.5 Hz, CH3C), 22.0 (d, JP, C 63.5 Hz, PCCH3), 1.7 ppm (s,
CH3Si); IR (C6D6): nÄ 2028 cmÀ1 (C C N).
1,2-Dihydro-1,2-azaphosphete 4b: 31P{1H} NMR (CDCl3): d 59.1 ppm;
1H NMR (CDCl3): d 3.61 (sept, JHH 6.6 Hz, 2H; CHN), 3.34 (sept d,
3
3JH,H 6.6 Hz, JPH 8.6 Hz, 2H; CHN), 2.34 (s, 6H; CH3N), 1.19(d,
3
3JHH 6.6 Hz, 6H; CH3CH), 1.18 (d, JH,H 6.6 Hz, 6H; CH3CH), 1.17 (d,
3
3JH,H 6.6 Hz, 6H; CH3CH), 1.11 (d, JH,H 6.6 Hz, 6H; CH3CH),
3
0.12 ppm (s, 9H; CH3Si); 13C{1H} NMR (CDCl3): d 146.9(d, JP, C
2
2
À
À
À
19.1 Hz, P C C), 123.6 (s, P C C ), 49.0 (s, CHN C ), 46.7 (d, JP, C
À
4.2 Hz, CHN P), 43.7 (brd, CH3N), 23.2 (s, CH3C), 21.9(s, CH3C), 2.1 ppm
3
(d, JP, C 5.8 Hz, CH3Si).
Ketenimine 7'c: Yellow oil (91% yield); 31P{1H} NMR (C6D6): d
53.1 ppm; 1H NMR (C6D6): d 3.60 (sept d, JH,H 6.8 Hz, JP, H
3
3
2
3
11.0 Hz, 4H; CHN), 3.27 (d, JP, H 10.2 Hz, 1H; PCH), 1.43 (d, JH,H
6.8 Hz, 12H; CH3CH), 1.42 (d, 3JH,H 6.8 Hz, 12H; CH3CH), 1.31 ppm (m,
21H; CH3CHSi); 13C{1H} NMR (C6D6): d 175.7 (d, JP, C 36.6 Hz,
2
2
1
PC C), 47.4 (d, JP, C 11.0 Hz, CHN), 27.4 (d, JP, C 8.8 Hz, PC), 24.7 (d,
2JP, C 5.8 Hz, CH3C), 24.5 (d, JP, C 9.2 Hz, CH3C), 18.3 (s, CH3CSi),
2
12.7 ppm (s, CHSi); IR (C6D6): nÄ 2044 cmÀ1 (C C N).
Ketenimine 7'd: Yellow oil (69% yield); 31P{1H} NMR (C6D6): d
61.4 ppm; 1H NMR (C6D6): d 3.46 (sept d, JH,H 6.6 Hz, JP,H 11.0 Hz,
3
3
3
3
4H; CHN), 1.86 (d, JP, H 9.4 Hz, 3H; PCCH3), 1.27 (d, JH,H 6.6 Hz,
3
12H; CH3CH), 1.25 (d, JH,H 6.6 Hz, 12H; CH3CH), 1.11 (s, 18H;
[11] D. Lentz, M. Anibaro, D. Preugschat, G. Bertrand, J. Fluorine Chem.
1999, 89, 73.
CH3CHSi), 1.04 ppm (s, 3H; CHSi); 13C{1H} NMR (C6D6): d 184.7 (d,
2JP, C 11.1 Hz, PC C), 48.7 (d, JP, C 11.8 Hz, CHN), 40.9(d, JP, C
2
1
[12] a) R. Appel, V. Barth, F. Knoch, Tetrahedron Lett. 1980, 21, 1923;
b) R. Appel, V. Barth, F. Knoch, Chem. Ber. 1983, 116, 9 38; c) N.
Maigrot, C. Charrier, L. Ricard, F. Mathey, Polyhedron 1990, 9, 1363;
d) W. W. Schoeller, U. Tubbesing, A. B. Rozhenko, Eur. J. Inorg.
Chem. 1998, 951; e) O. Schmidt, A. Fuchs, D. Gudat, M. Nieger, W.
Hoffbauer, E. Niecke, W. W. Schoeller, Angew. Chem. 1998, 110, 9 9 5;
Angew. Chem. Int. Ed. Engl. 1998, 37, 949; f) E. Niecke, A. Fuchs, M.
2
2
4.7 Hz, PC), 25.8 (d, JP, C 8.0 Hz, CH3C), 25.3 (d, JP, C 7.0 Hz, CH3C),
2
20.1 (d, JP, C 6.4 Hz, PCCH3), 17.1 (s, CH3CSi), 13.5 ppm (s, CHSi); IR
(C6D6): nÄ 2026 cmÀ1 (C C N).
1,4-Azaphosphabutadiene 8b: Yellow oil (58% yield); 31P{1H} NMR
(C6D6): d 113.1 ppm; 1H NMR (C6D6): d 4.30 (sept, JH,H 6.6 Hz,
3
2H; CHN), 3.28 (sept, 3JH,H 6.6 Hz, 2H; CHN), 2.66 (s, 6H; CH3N), 1.36
5310
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Chem. Eur. J. 2002, 8, No. 23