Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

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Table 2. Selected bond angles (º) in complexes 13⋅H2O⋅CH2Cl2 and 17 N5-Ni-N1 175.7(1) N5-Ni-O3 78.5(1) N1-Ni-O3 100.6(1) N5-Ni-O1 97.4(1) 13⋅H2O⋅CH2Cl2 17 N1-Ni-O1 78.3(1) 77.96(5) O1-Ni-O3 86.7(1) N5-Ni-N7 79.3(2) N1-Ni-N7 101.0(2) O3-Ni-N7 156.6(1) O1-Ni-N7 89.0(2) N5-Ni-N3 104.6(2) N1-Ni-N3 79.6(2) 81.58(6) O1-Ni-N3 156.9(1) 156.73(5) N3-Ni-N7 101.7(2) Cl1-Ni-Cl2 103.43(2) Cl1-Ni-N1 97.78(4) Cl2-Ni-N1 157.78(5) Cl2-Ni-O1 98.28(3) Cl2-Ni-N3 96.47(4) Cl1-Ni-N3 95.79(4) Cl1-Ni-O1 98.15(4) 3. Catalytic Oligomerization of Ethylene Chapitre I The precatalysts 13-17 have been tested in the presence of variable amounts of AlEtCl2 or MAO as cocatalyst and showed high activities for the dimerization and trimerization of ethylene (Tables 3 and 4).The results were compared with those obtained with NiCl2(PCy3)2, a typical α-olefin dimerization catalyst. 49,50 It was interesting to determine the fractions of the different C6 oligomers formed by chain growth or by reinsertion of 1-butene or 2-butene (Tables 5 and 6). Depending on the nature of their insertion (2,1- or 1,2-insertion) and on which C-H bond undergoes agostic interaction 12
Chapitre I with the metal, 51-54 two schemes can explain the formation of cis- and trans-2-hexene, cis- and trans-3-hexene and 2-ethylbut-2-ene from 1-butene (Scheme 4) and the formation of cis- and trans-3-methylpent-2-ene and 3-methylpent-1-ene from 2-butene (Scheme 5). 1-Hexene is formed by a chain growth mechanism its Ni-catalyzed isomerization leads to 2-hexene and 3-hexene. 55 A comparison of the various catalytic results should indicate the influence of (i) the nature of the donor function in the complexing ligand arm, (ii) the increase in metal coordination number resulting from the presence of the complexing arm, by comparison with the properties of 4, (iii) the metal coordination geometry, (iv) the nature of the cocatalyst and (v) the lifetime of the catalyst. Scheme 4. Hexenes resulting from the reinsertion of 1-butene. The stereochemical information is not illustrated: agostic interactions with diastereotopic CH2 protons afford the cis or trans isomers. 13
Page 1 and 2: THESE Présentée à l’Universit
Page 3 and 4: Lisa, Mireia, Anja, Fredy, Shuanmin
Page 5 and 6: SOMMAIRE Composition du document et
Page 7 and 8: 6. reference 32 Chapitre V Synthesi
Page 9 and 10: Composition du document et organisa
Page 11 and 12: Introduction La dynamique économiq
Page 13 and 14: Introduction La première étape co
Page 15 and 16: Introduction 26, 68-70 Des mécanis
Page 17 and 18: R R' P Ni Ph O B(Arf) R = R' = t-Bu
Page 19 and 20: Introduction Activés par des alkyl
Page 21 and 22: 18 19 20 21 22 23 24 25 26 27 28 29
Page 23 and 24: 88 89 90 91 92 93 94 95 96 97 98 99
Page 25 and 26: Chapitre I Nickel Complexes with Fu
Page 27 and 28: Abstract Chapitre I Zwitterionic N,
Page 29 and 30: R HN O 1 O NH R Ph Ph 3P Ni R N O 2
Page 31 and 32: Chapitre I As shown in Figure 1, th
Page 33 and 34: Chapitre I Figure 3. Views of the s
Page 35: Chapitre I Figure 6. View of the ar
Page 39 and 40: Chapitre I these conditions, precat
Page 41 and 42: Chapitre I The precatalyst 13-17 ha
Page 43 and 44: Chapitre I Table 5. Catalytic Data
Page 45 and 46: TOF mol C2H4 / mol Ni.h -1 20000 15
Page 47 and 48: Chapitre I (s, OCH2), 81.27 (s, N
Page 49 and 50: Chapitre I atoms introduced as fixe
Page 51 and 52: Chapitre I (51) Tempel, D. J.; Broo
Page 53 and 54: Abstract Chapitre II The dinuclear
Page 55 and 56: Chapitre II Other neutral nickel co
Page 57 and 58: OH 4 O N 4 13 OH N + 2 NiCl 2 + 2 N
Page 59 and 60: N2-Ni1-Cl1 169.45(12) 89.35(15) N2-
Page 61 and 62: Table 2. Selected bond distances an
Page 63 and 64: Chapitre II solubility of 15 in chl
Page 65 and 66: Chapitre II Table 4. Catalytic Data
Page 67 and 68: Chapitre II Table 5. Comparative Ca
Page 69 and 70: mass % of C4 olefins 100 90 80 70 6
Page 71 and 72: 5. Experimental Chapitre II The 1 H
Page 73 and 74: Chapitre II a dark green powder. Yi
Page 75 and 76: Chapitre II 17 W. Keim, J. Mol. Cat
Page 77 and 78: 7. Supporting information Table S1.
Page 79 and 80: Chapitre III Unprecedented Tetranuc
Page 81 and 82: Abstract Chapitre III Reactions of
Page 83 and 84: Chapitre III distorted octahedral c
Page 85 and 86: data for 2a⋅2CH2Cl2: 1.41 and for
Page 87 and 88:
Chapitre III indicate that subtle d
Page 89 and 90:
SUPPORTING INFORMATION FOR Chapitre
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Chapitre III by filtration. The sol
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Chapitre III 4 was prepared followi
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[S- ] 3. Evans method 2 Chapitre II
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Chapitre III Application Constructe
Page 99 and 100:
Chapitre III [S-5] J. K. McCusker,
Page 101 and 102:
Abstract Chapitre IV The P,N-type l
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Chapitre IV Scheme 1. Complexes wit
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12 PPh 2 N O N PPh 2 O N 13 P 14 15
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Chapitre IV Although some nickel co
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Scheme 2. Representation of the squ
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Chapitre IV The analysis of the dif
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Chapitre IV Table 4. Catalytic Data
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mass % of 1-butene 100 90 80 70 60
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Chapitre IV Table 6. Catalytic Data
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ef Scheme 3. Proposed pathways to e
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4. Conclusion Chapitre IV New P,N l
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Chapitre IV SiCH3), 30.25 (s, SiCH2
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Chapitre IV 122.3 (s, Py), 122.5 (d
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[Ni(µ-Cl)2{(pyridin-2-yl) methanol
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Chapitre IV mmol of Ni complex or 1
Page 131 and 132:
6. References (1) Ziegler, K.; Holz
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Chapitre IV (44) Bluhm, M. E.; Foll
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Chapitre V Synthesis and catalytic
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Chapitre V to 16, the IR spectrum o
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Chapitre V activated by MAO (Scheme
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2 OH N + PPhCl 2 NEt 3 - (HNEt 3)Cl
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Chapitre V Slow diffusion of heptan
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Chapitre V Figure 3. ORTEP view of
Page 147 and 148:
Chapitre V tridentate ligand but wi
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Chapitre V spin system 1) and 3.06
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Chapitre V This establishes the coo
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TOF (mol C2H4/(mol Ni.h)) 90000 800
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% mass of 1-butene 80 70 60 50 40 3
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Chapitre V cyclic voltammograms of
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Chapitre V A n-BuLi solution (64.0
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Chapitre V IR (KBr): 1658 (vs), 147
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Chapitre V To a solution of (2-oxaz
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Chapitre V Synthesis of [Co{bis(1-(
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Chapitre V 30 bar working pressure
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6. References 1 2 3 4 5 6 7 8 9 10
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67 68 69 70 71 72 73 74 75 76 77 78
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Abstract Chapitre VI The β-keto ph
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Ph O 3 toluene PPh3 + Ni(COD) 2 + P
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Chapitre VI The synthesis of β-ket
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Table 1 Selected bond distances (Å
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Ph O toluene PR2R' + Ni(COD) 2 + C5
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4. Conclusion Chapitre VI The β-ke
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Chapitre VI and the solution was st
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Chapitre VI (s, p-C of OC-Ph), 131.
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Chapitre VI To a solution of 13.000
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Chapitre VI the solvents under redu
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Chapitre VI Crystal Structure Deter
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23 F. A. Hicks and M. Brookhart, Or
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Chapitre VII Réarrangement type Ar
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1. Introduction Chapitre VII Brookh
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N OPPh 2 OPPh 2 + NiCl2(DME) N O Ph
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Chapitre VII mécanisme apparenté
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[Ni{2,6-bis((diphenylphosphinito)me
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Résumé et Conclusion générale
Page 209 and 210:
Chapitre II Résumé et conclusion
Page 211 and 212:
Résumé et conclusion générale P
Page 213 and 214:
Résumé et conclusion générale l
Page 215 and 216:
Chapitre VII Résumé et conclusion
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Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

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