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N.J. Rahier et al. / Tetrahedron 64 (2008) 6645–6650
4. (a) Baldwin, R. A.; Washburn, R. M. J. Am. Chem. Soc. 1961, 83, 4466; (b) Baldwin,
R. A.; Washburn, R. M. J. Org. Chem. 1965, 30, 3860; (c) Wiegra¨be, W.; Bock, H.
Chem. Ber. 1968, 101, 1414; (d) L’Abbe´, G.; Ykman, P.; Smets, G. Tetrahedron 1969,
25, 5421; (e) Khodak, A. A.; Gilyarov, V. A.; Kabachnik, M. I. J. Gen. Chem. USSR
1976, 46, 1628; (f) Khodak, A. A.; Gilyarov, V. A.; Kabachnik, M. I. Zh. Obshch.
Khim. 1976, 46, 1672; (g) Gilyarov, V. A.; Matrosov, E. I.; Kabachnik, M. I. Bull.
Acad. Sci. USSR Div. Chem. Sci. 1991, 40, 628; (h) Gilyarov, V. A.; Matrosov, E. I.;
Kabachnik, M. I. Izv. Akad Nauk USSR, Ser. Khim. 1991, 3, 713; (i) Riesel, L.; Friebe,
R.; Bergemann, A.; Sturm, D. Heteroat. Chem. 1991, 2, 469; (j) Riesel, L.; Friebe, R.
Z. Anorg. Allg. Chem. 1991, 604, 85; (k) Riesel, L.; Friebe, R.; Sturm, D. Phosphorus,
Sulfur Silicon Relat. Elem. 1993, 76, 207.
5. Baldwin, R. A. J. Org. Chem. 1965, 30, 3866.
6. Appel, R.; Einig, H. Chem. Ber. 1975, 108, 914.
7. Roesky, H. W.; Grimm, L. F. Chem. Ber. 1969, 102, 2319.
8. Bittner, S.; Assaf, Y.; Krief, P.; Pomerantz, M.; Ziemnicka, B. T.; Smith, C. G. J. Org.
Chem. 1985, 50, 1712.
The combined organic fraction was dried (Na2SO4), filtered, and
concentrated under reduced pressure. The residue was purified by
chromatography on silica. Gradient elution with 0–5% methanol in
methylene chloride afforded 5b as an off-white solid. Yield 30%. Mp
(dioxane) 190–191 ꢁC (lit.9b 193 ꢁC). MS [FABþ]: m/z¼876 [MþHþ].
IR (KBr) 3060 (m), 1435 (vs), 1230 (vs, P]N), 1190 (s), 1115 (vs,
P]O), 720 (vs), 540 (vs). 1H NMR (CDCl3)
d
¼7.17–7.47 (m, 45H,
C6H5). 13C NMR (CDCl3)
d
¼128.30 (d, 3JPC¼12.7 Hz, m-C), 130.35 (dd,
1
3
4
0
JPC¼105.5 Hz, JP C¼4.3 Hz, ipso-C), 131.64 (d, JPC¼2.6 Hz, p-C),
132.80 (d, JPC¼11.2 Hz, o-C). 31P NMR (CDCl3)
d
¼0.45 (q, JPP
¼
2
2
0
2
10.0 Hz, P0), 8.74 (d, JPP ¼10.0 Hz, P). C54H45N3OP4 (875.88) calcd C,
0
74.05; H, 5.18; N, 4.80. Found: C, 69.41; H, 5.06; N, 4.44.
9. (a) Zhmurova, I. N.; Martynyuk, A. P.; Shtepanek, A. S.; Zasorina, V. A.; Kukhar,
V. P. J. Gen. Chem. USSR 1974, 44, 76; Zh. Obshch. Khim. 1974, 44, 79; (b) Shte-
panek, A. S.; Zasorina, V. A.; Zhmurova, I. N.; Martnyuk, A. P. J. Gen. Chem. USSR
1975, 45, 999; Zh. Obshch. Khim. 1975, 52, 1012; (c) Biddlestone, M.; Shaw, R. A.
J. Chem. Soc., Dalton Trans. 1975, 2527; (d) Zasorina, V. A.; Shtepanek, A. S.;
Pinchuk, A. M. J. Gen. Chem. USSR 1982, 52, 941; Zh. Obshch. Khim. 1982, 52,
1081; (e) Pinchuk, A. M.; Zasorina, V. A.; Shtepanek, A. S.; Rozhkova, Z. A.;
Solotnov, A. F.; Raevskii, O. A. J. Gen. Chem. USSR 1983, 53, 1816; Zh. Obshch.
Khim. 1983, 53, 2012; (f) Goumri, S.; Lacassin, F.; Baceiredo, A.; Bertrand, G.
Heteroat. Chem. 1996, 6, 403.
4.5.2. N,N0,N00-(Phosphinetriyl)tris-triphenylphosphinimine
hydrochloride (6)9b,f
To a suspension of Ph3P]NLi (1.19 g, 4.2 mmol) in THF (50 mL)
prepared as described above was added dropwise at room tem-
perature, via a syringe, freshly distilled phosphorus trichloride
(122 mL, 1.40 mmol). After stirring at room temperature for 30 min,
a white precipitate was filtered off and washed with THF to give 6 as
an off-white solid. Yield 95%. Mp 52–53 ꢁC (lit.9f 49–50 ꢁC). MS
[FABþ]: m/z¼859 [MꢀCl]. IR (KBr) 3025 (m), 1455 (m), 1235 (s,
10. Johnson, A. W. Ylides and Imines of Phosphorus; John Wiley and Sons: New York,
NY, 1993; p 438.
11. (a) Mardersteig, H. G.; Meinel, L.; No¨th, H. Z. Anorg. Allg. Chem. 1969, 368, 254;
(b) Flindt, E.-P. Z. Anorg. Allg. Chem. 1978, 447, 97; (c) Mazieres, M. R.; Roques, C.;
Sanchez, M.; Majoral, J. P.; Wolf, R. Tetrahedron 1987, 43, 2109; (d) Rivard, E.;
Huynh, K.; Lough, A. J.; Manners, I. J. Am. Chem. Soc. 2004, 126, 2286.
12. Mardersteig, H. G.; No¨th, H. Z. Anorg. Allg. Chem. 1970, 375, 272.
13. Fluck, E.; Ho¨sle, R. Z. Anorg. Allg. Chem. 1979, 458, 103.
P]N), 1140 (m), 720 (w), 565 (s). 1H NMR (CDCl3)
d
¼7.46 (dd,
1
3
JPH¼579.5 Hz, JP H¼5.5 Hz, 1H), 7.29–7.55 (m, 45H, C6H5P). 13C
0
3
NMR (CDCl3)
d
¼128.69 (d, JPC¼12.7 Hz, m-C), 129.27 (dd,
1
3
2
0
JPC¼105.1 Hz, JP C¼3.9 Hz, ipso-C), 132.29 (d, JPC¼10.8 Hz, o-C),
132.47 (d, 4JPC¼2.2 Hz, p-C). {1H}31P NMR (CDCl3)
d
¼ꢀ12.53 (s, P0),
14. (a) Appel, R.; Bu¨chler, G. Z. Anorg. Allg. Chem. 1963, 320, 3; (b) Appel, R.;
Mathieson, O. Chemical Corporation. U.S. Patent 3,358,021, 1967; Chem. Abstr.
1968, 69, 10212j.
12.69 (s, P). 31P NMR (CDCl3)
(s, P).
d
¼ꢀ12.53 (d, 1JP H¼579.5 Hz, P0), 12.69
0
¨
15. (a) Emsley, J.; Moore, J.; Udy, P. B. J. Chem. Soc. A 1971, 2863; (b) Yilmaz, O.; Aslan,
¨
F.; Oztu¨rk, A. I.; Vanli, N. S.; Kirbag, S.; Arslan, M. Bioorg. Chem. 2002, 30, 303.
16. The synthesis of Ph3P]N]P(Ni-Pr2)2 hasbeen reported by thisway(from ClP(Ni-
Pr2)2). Gru¨tzmacher, H.; Pritzkow, H.; Stephan, M. Tetrahedron 1990, 46, 2381.
17. (a) Schwesinger, R. Chimia 1985, 39, 269; (b) Schwesinger, R.; Schlemper, H.
Angew. Chem., Int. Ed. Engl. 1987, 26, 1167; (c) Schwesinger, R.; Willaredt, J.;
Schempler, H.; Keller, M.; Schmitt, D.; Fritz, H. Chem. Ber. 1994, 127, 2435; (d)
Schwesinger, R.; Schempler, H.; Hasenfratz, C.; Willaredt, J.; Dambacher, T.;
Breuer, T.; Ottaway, C.; Fletschinger, M.; Boele, J.; Fritz, H.; Putzas, D.; Rotter, H.
W.; Bordwell, F. G.; Satish, A. V.; Ji, G.-Z.; Peters, E.-M.; Peters, K.; von Schnering,
H. G.; Walz, L. Liebigs Ann. 1996, 1055.
18. (a) Schmidt, H.; Lensik, C.; Xi, S. K.; Verkade, J. G. Z. Anorg. Allg. Chem. 1989, 578,
75; (b) Lensik, C.; Xi, S. K.; Daniels, L. M.; Verkade, J. G. J. Am. Chem. Soc. 1989,
111, 3478; (c) Kisanga, P. B.; Verkade, J. G.; Schwesinger, R. J. J. Org. Chem. 2000,
65, 5431; (d) Verkade, J. G.; Kisanga, P. B. Tetrahedron 2003, 59, 7819; (e)
Verkade, J. G. Top. Curr. Chem. 2003, 223, 1.
19. Taillefer, M.; Rahier, N.; Hameau, A.; Volle, J.-N. Chem. Commun. 2006, 3238.
20. Taillefer, M.; Xia, N.; Ouali, A. Angew. Chem., Int. Ed. 2007, 46, 934 and references
therein.
21. Cristau, H. J.; Kadoura, J.; Chiche, L.; Torreilles, E. Bull. Soc. Chim. Fr. 1989, 4, 515.
22. Huynh, K.; Rivard, E.; LeBlanc, W.; Blackstone, V.; Lough, A. J.; Manners, I. Inorg.
Chem. 2006, 45, 7922.
4.5.3. N,N0,N00-(Phosphinetriyl)tris-triphenylphosphinimine (5a)11
and N,N0,N00-(thionophosphoretriyl) tris-triphenylphosphinimine
(5c)29
To a solution of N,N0,N00-(phosphinetriyl)tris-triphenylphosphin-
imine hydrochloride 6 (0.45 g, 0.5 mmol) in DMSO (10 mL) was
added dropwise at room temperature n-butyllithium in hexanes
(313 mL, 0.5 mmol). After stirring at room temperature for 30 min,
an in situ 31P NMR spectra showed the quantitative formation of
N,N0,N00-(phosphinetriyl)tris-triphenylphosphinimine 5a. 31P NMR
2
(DMSO)
d
¼ꢀ0.13 (br d, 2Jpp ¼27.1 Hz, P), 101.19 (br q, Jpp ¼27.1 Hz,
0
0
P0). To the resulting mixture was added sulfur (32 mg, 1.0 mmol).
After stirring at room temperature, an in situ 31P NMR spectra
showed the formation of 6 (12%), 5b (52%) and 5c (N,N0,N00-(thio-
nophosphoretriyl)tris-triphenylphosphinimine); yield 24%; 31P
2
NMR (DMSO)
d
¼ꢀ4.21 (q, 2JPP ¼3.1 Hz, P ), 12.70 (d, JPP ¼3.1 Hz, P).
0
0
0
23. Washburn, R. M.; Baldwin, R. A. American Potash and Chemical Corporation.
U.S. Patent 3,189,564, 1965; Chem. Abstr. 1965, 63, 54825.
24. Riesel, L.; Helbing, R. Z. Anorg. Allg. Chem. 1992, 617, 148.
25. (a) Bartel, K.; Von Werner, K.; Beck, W. J. Organomet. Chem. 1983, 243, 79; (b)
Larre, C.; Donnadieu, B.; Caminade, A.-M.; Majoral, J.-P. Eur. J. Inorg. Chem. 1999,
4, 601.
References and notes
1. Schmidbaur, H.; Jonas, G. Chem. Ber. 1967, 100, 1120.
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27. (a) Paciorek, K. L. Inorg. Chem. 1964, 3, 96; (b) Darensbourg, D. J.; Pala, M.;
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Smith, A. J. Chem. Soc., Perkin Trans. 1 1986, 377; (e) Cristau, H. J.; Manginot, E.;
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Heteroat. Chem. 2003, 14, 138.
28. (a) Noeth, H.; Schraegle, W. Z. Naturforsch. 1961, 16b, 473; (b) Mashlyakovskii,
L. N.; Ionin, B. I. Zh. Obshch. Khim. 1965, 35, 1577.
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Chem. 2006, 10, 2051.
3. (a) Taillefer, M.; Inguimbert, N.; Ja¨ger, L.; Merzweiler, K.; Cristau, H. J. Chem.
Commun. 1999, 565; (b) Cristau, H. J.; Jouanin, I.; Taillefer, M. J. Organomet.
Chem. 1999, 584, 68; (c) Cristau, H. J.; Taillefer, M.; Jouanin, I. Synthesis 2001, 69;
(d) Taillefer, M.; Cristau, H. J.; Fruchier, A.; Vicente, V. J. Organomet. Chem. 2001,
624, 30; (e) Ja¨ger, L.; Maurizot, V.; Wagner, C.; Taillefer, M.; Cristau, H. J. Challenges
for Coordination Chemistry in the New Century; Milan Melnik and Anton Sirota:
Bratislava, 2001; p 195; (f) Cristau, H. J.; Taillefer, M.; Rahier, N. J. Organomet.
Chem. 2002, 646, 94; (g) Taillefer, M.; Cristau, H. J. Top. Curr. Chem. 2003, 229, 41;
(h) Inguimbert, N.; Ja¨ger, L.; Taillefer, M.; Biedermann, M.; Cristau, H. J. Eur. J. Org.
Chem. 2004, 23, 4870.