Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

Chapitre I
(s, OCH2), 81.27 (s, N ⋅⋅⋅ C ⋅⋅⋅ C), 99.01 (s, O ⋅⋅⋅ C ⋅⋅⋅ C), 156.79 (s, N ⋅⋅⋅ C), 172.23 (s, O ⋅⋅⋅ C); Anal.
Calcd. for C18H28N4O4⋅0.5H2O: C, 57.89; H, 7.83; N, 15.00. Found: C, 57.75; H, 7.80; N,
15.36.
Complex 13. Ligand 9 (1.12 g, 4.0 mmol) was dissolved in dichloromethane (200 ml) and 0.5
equiv solid [Ni(acac)2] (0.55 g, 2.0 mmol) was then added to the solution in one portion. After
the solution was stirred at room temperature for 3 h, the solvent was concentrated to ca. 20 ml
under vacuum and the red crystalline complex 13 was obtained by precipitation from a
mixture of dichloromethane and pentane. Yield: 92%. Mass spect. (MALDI-TOF + ): m/z =
617.3[M+1] + ; Anal. Calcd. for C28H46N8NiO4⋅H2O⋅CH2Cl2: C, 48.35; H, 7.00; N, 15.56.
Found: C, 48.65; H, 7.12; N, 15.78.
Complex 14. The synthetic procedure was similar to that described for complex 13 but using
ligand 10 instead of 9. Yield: 88%. Mass spect. (MALDI-TOF + ): m/z = 617.3 [M+1] + ; Anal.
Calcd. for C28H46N8NiO4⋅0.5H2O ⋅0.5CH2Cl2: C, 51.18; H, 7.23; N, 16.75. Found: C, 51.06;
H, 7.28; N, 17.04.
Complex 15. The synthetic procedure was similar to that described for complex 13 but using
ligand 11 instead of 9. Yield: 91%. Mass spect. (MALDI-TOF + ): m/z = 565.2 [M+1] + ; Anal.
Calcd. for C24H34N4NiO8: C, 51.00; H, 6.06; N, 9.91. Found: C, 50.91; H, 6.03; N, 9.85.
Complex 16. The synthetic procedure was similar to that described for complex 13 but using
ligand 12 instead of 9. Yield: 93%. Mass spect. (MALDI-TOF + ): m/z = 785.3 [M+1] + ; Anal.
Calcd. for C36H54N8NiO8⋅0.5H2O: C, 54.42; H, 6.98; N, 14.10. Found; C, 54.37; H, 7.03; N,
13.91.
Complex 17. To a solution of ligand 9 (0.28 g, 1.0 mmol) in methanol (30 ml) was added 1
equiv NiCl2⋅6H2O (0.24 g, 1.0 mmol) and the reaction mixture was stirred for 3 h. Complex
17 was obtained as a purple crystalline solid by slow diffusion of ether into the reaction
mixture. Yield: 71%. Ms (MALDI-TOF - ): m/z: 409.1 [M-1] - ; Anal. Calcd. for
C14H24Cl2N4NiO2: C, 41.02; H, 5.90; N, 13.67. Found: C, 40.81; H, 6.11; N, 13.33.
Oligomerization of Ethylene: All catalytic reactions were carried out in a magnetically
stirred (900 rpm) 145 ml stainless steel autoclave. A 125 ml glass container was used to
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