4a (157 mg, 80%). HR-EI-MS: 684.9825 (M; C30H33NP2NiBr2; calc.
684.9809). 606.0633 (M; C30H33NP2NiBr; calc. 606.0625). Anal. Calc. for
C30H33NP2NiBr2: C, 52.37; H, 4.83; N, 2.04. Found: C, 52.42; H, 4.93; N,
2.18%. 4c (154 mg, 78%). HR-EI-MS: 690.9351 (M; C31H27NP2NiBr2; calc.
690.9339). 612.0148 (M; C31H27NP2NiBr; calc. 612.0156). Anal. Calc. for
C31H27NP2NiBr2: C, 53.65; H, 3.92; N, 2.02. Found: C, 53.72; H, 3.81; N,
2.37%. 5a (175 mg, 82%) HR-EI-MS: 746.9969 (M; C35H35NP2NiBr2; calc.
746.9965). 668.0761 (M; C35H35NP2NiBr2; calc. 668.0782). Anal. Calc. for
C35H35NP2NiBr2: C, 56.04; H, 4.70; N, 1.87. Found: C, 56.19; H, 4.83; N,
2.06%. 5b (161 mg, 78%). HR-EI-MS: 718.9645 (M; C33H31NP2NiBr2;
calc. 718.9652), 639.0402 (M; C33H31NP2NiBr; calc. 639.0390). Anal. Calc.
for C33H31NP2NiBr2: C, 54.89; H, 4.33; N, 1.94. Found: C, 54.64; H, 4.24;
N, 1.89%. 5c (147 mg, 70%). HR-EI-MS: 732.9783 (M; C34H33NP2NiBr2;
calc. 732.9809), 654.0595 (M; C34H33NP2NiBr; calc. 654.0625). Anal. Calc.
for C34H33NP2NiBr2: C, 55.48; H, 4.52; N, 1.90. Found: C, 55.28; H, 4.34;
N, 1.81%. 5d (143 mg, 75%). HR-EI-MS: 665.0091 (M; C28H37NP2NiBr2;
calc. 665.0122), 586.0948 (M; C28H37NP2NiBr; calc. 586.0938). Anal. Calc.
for C28H37NP2NiBr2: C, 50.34; H, 5.58; N, 2.10. Found: C, 50.43; H, 5.47;
N, 2.20%. 6 (151 mg, 71%). HR-EI-MS: 704.9456 (M; C29H32NP2NiBr2;
calc. 704.9496), 626.0304 (M; C29H32NP2NiBr; calc. 626.0312). Anal. Calc.
for C29H32NP2NiBr2: C, 54.28; H, 4.13; N, 1.98. Found: C, 54.35; H, 4.22;
N, 1.72%.
quantitative GC, first calibrated with authentic samples (except in the case
of butene for which the calibration was based upon the response factor of
n-pentane).
1 D. Vogt, in Applied Homogeneous Catalysis with Organometallic
Compounds, ed. B. Cornils and W. A. Hermann, Wiley, Weinheim,
1996, p. 245.
2 Y. Chauvin and H. Olivier, in Applied Homogeneous Catalysis with
Organometallic Compounds, ed. B. Cornils and W. A. Hermann, Wiley,
Weinheim, 1996, p. 258.
3 A. Bre, Y. Chauvin and D. Commereuc, New J. Chem., 1986, 10, 535.
4 (a) G. J. P. Britovsek, V. C. Gibson, B. S. Kimberley, S. Mastroianni,
C. Redshaw, G. A. Solan, A. J. P. White and D. J. Williams, J. Chem.
Soc., Dalton Trans., 2001, 1639; (b) D. S. McGuinness, V. C. Gibson
and J. W. Steed, Organometallics, 2004, 23, 12716; (c) K. P. Tellman,
V. C. Gibson, A. J. P. White and D. J. Williams, Organometallics, 2005,
24, 280.
5 F. Speiser, P. Braunstein and L. Saussine, Acc. Chem. Res., 2005, 38,
784, and references herein.
6 M. Sauthier, F. Leca, R. F. de Souza, K. Bernardo-Gusmao, L. F. T.
Queiroz, L. Toupet and R. Reau, New J. Chem., 2002, 26, 630.
7 M. Lejeune, D. Semeril, C. Jeunesse, D. Matt, F. Peruch, P. L. Lutz and
L. Ricard, Chem.–Eur. J., 2004, 10, 5354.
§ Crystal structures of complexes 4c and 5a,c,d will be published elsewhere,
for crystal structure of 4b see ref. 10a.
8 Z. Q. Weng, S. Teo, L. L. Koh and T. S. A. Hor, Chem. Commun.,
2006, 1319.
" C33H31Br2NNiP2, Mr = 722.06, monoclinic, space group P21/c, a =
9.087(1), b = 16.597(1), c = 21.913(1) s, b = 110.180(1)u, V = 3102.0(4) s3,
T = 150.0(1) K, Z = 4, F(000) = 1456, m = 3.328 cm21, 10809 reflections
measured, 6329 unique data, Rint = 0.0279. Final R1 = 0.0315 (wR2 =
0.0652). CCDC 631235. For crystallographic data in CIF or other
electronic format see DOI: 10.1039/b618401d.
I General oligomerisation procedure: All catalytic reactions were carried out
in a magnetically stirred 120 mL stainless steel autoclave, equipped with a
pressure gauge and needle valves for injections. The interior of the
autoclave was protected from corrosion by a Teflon/protective coating. A
typical reaction was performed by introducing in the reactor under nitrogen
atmosphere the nickel complex (20 mmol) and 30 mL of toluene. After
injection of the MAO solution (300 equiv., 4 mL), the reactor was
immediately brought to the desired working temperature and pressure, and
continuously fed by ethylene using a reserve bottle. The reaction was
stopped by closing the ethylene supply, cooling the system to 270 uC. After
the pressure in the reactor has decreased to atmospheric pressure, the
reaction was quenched by adding 1 mL of methanol. n-Heptane used as
internal standard was also introduced and the mixture was analysed by
9 N. Ajellal, M. C. A. Kuhn, A. D. G. Boff, M. Horner, C. M. Thomas,
J.-F. Carpentier and O. L. Casagrande, Organometallics, 2006, 25, 1213.
10 (a) L. Boubekeur, L. Ricard, N. Me´zailles and P. Le Floch,
Organometallics, 2005, 24, 1065; (b) L. Boubekeur, L. Ricard,
N. Me´zailles, M. Demange, A. Auffrant and P. Le Floch,
Organometallics, 2006, 25, 3091.
11 For the synthesis of iminophosphosphorane by the Staudinger reaction,
see for example: (a) H. Staudinger and J. Meyer, Helv. Chim. Acta, 1919,
2, 619–635; (b) Y. G. Gololobov, I. N. Zhmurova and L. F. Kasukhin,
Tetrahedron, 1981, 37, 437–472; (c) Y. G. Gololobov and L. F. Kasukhin,
Tetrahedron, 1992, 48, 1353–1406; (d) Ylides and Imines of Phosphorus,
ed. A. W. Johnson, Wiley, New York, 1993.
12 (a) F. Speiser, P. Braunstein and L. Saussine, Dalton Trans., 2004, 1539;
(b) F. Speiser, P. Braunstein and L. Saussine, Organometallics, 2004, 23,
2625.
13 P. Kuhn, C. Jeunesse, D. Semeril, D. Matt, P. Lutz and R. Welter,
Eur. J. Inorg. Chem., 2004, 4602.
1504 | Chem. Commun., 2007, 1502–1504
This journal is ß The Royal Society of Chemistry 2007