Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

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Chapitre V The catalytic results, presented in Table 5, showed that increasing the amount of cocatalyst produced more active systems but less selective in C4 olefins and in 1-butene. Very active system the isomerization of 1-butene in 2-butene and favored the reinsertion of 1-butene and 2-butene to form C6 oligomers. 76 Some tetrahedral iron(II) complexes have shown good activities in oligomerization and polymerization of ethylene 72, 73 and it was therefore interesting to test 12 with different cocatalysts and study its reactivity. However, activities of 12 with 200 equiv. of MAO or 6 equiv. of AlEtCl2 were very low and only traces of butenes were detected by gas chromatography. The hexacoordinated mononuclear iron complexes 10 and 11 containing two ligands around the metal centre showed no activity with MAO or AlEtCl2 as cocatalyst, perhaps because the coordination sphere of the iron center in saturated which disfavors ethylene coordination to the metal centre. A similar situation was observed with other inactive 77, 78 iron complexes containing two C,N,C pincer ligands. Table 5. Comparative Catalytic Data for Complexes 6, 8 and 9 in the Oligomerization of Ethylene a, b with AlEtCl2 as Cocatalyst. EADC Selectivity (mass %) (equiv) C4 C6 C8 Productivity [g C2H4/(g Ni·h)] TOF [mol C2H4/(mol Ni·h)] α-olefin (C4) (mol %) 6 6 53 43 4 26400 55600 8 0.57 6 10 54 42 4 29500 61800 9 0.55 8 6 90 10
TOF (mol C2H4/(mol Ni.h)) 90000 80000 70000 60000 50000 40000 30000 20000 10000 0 2 Equiv of AlEtCl2 4 6 10 6 8 9 ref Chapitre V Figure 7. Catalytic activities of the complexes 6, 8 and 9 in the oligomerization of ethylene using AlEtCl2 as cocatalyst, Ref: [NiCl2(Pn-Bu3)2]. % mass of 1-butene 35 30 25 20 15 10 5 0 2 Equiv of AlEtCl2 4 6 10 6 8 9 ref Figure 8. Selectivity of the complexes 6, 8 and 9 for 1-butene using AlEtCl2 as cocatalyst, Ref: [NiCl2(Pn-Bu3)2]. 19
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THESE Présentée à l’Universit
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Lisa, Mireia, Anja, Fredy, Shuanmin
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SOMMAIRE Composition du document et
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6. reference 32 Chapitre V Synthesi
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Composition du document et organisa
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Introduction La dynamique économiq
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Introduction La première étape co
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Introduction 26, 68-70 Des mécanis
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R R' P Ni Ph O B(Arf) R = R' = t-Bu
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Introduction Activés par des alkyl
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18 19 20 21 22 23 24 25 26 27 28 29
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88 89 90 91 92 93 94 95 96 97 98 99
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Chapitre I Nickel Complexes with Fu
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Abstract Chapitre I Zwitterionic N,
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R HN O 1 O NH R Ph Ph 3P Ni R N O 2
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Chapitre I As shown in Figure 1, th
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Chapitre I Figure 3. Views of the s
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Chapitre I Figure 6. View of the ar
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Chapitre I with the metal, 51-54 tw
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Chapitre I these conditions, precat
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Chapitre I The precatalyst 13-17 ha
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Chapitre I Table 5. Catalytic Data
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TOF mol C2H4 / mol Ni.h -1 20000 15
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Chapitre I (s, OCH2), 81.27 (s, N
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Chapitre I atoms introduced as fixe
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Chapitre I (51) Tempel, D. J.; Broo
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Abstract Chapitre II The dinuclear
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Chapitre II Other neutral nickel co
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OH 4 O N 4 13 OH N + 2 NiCl 2 + 2 N
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N2-Ni1-Cl1 169.45(12) 89.35(15) N2-
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Table 2. Selected bond distances an
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Chapitre II solubility of 15 in chl
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Chapitre II Table 4. Catalytic Data
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Chapitre II Table 5. Comparative Ca
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mass % of C4 olefins 100 90 80 70 6
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5. Experimental Chapitre II The 1 H
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Chapitre II a dark green powder. Yi
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Chapitre II 17 W. Keim, J. Mol. Cat
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7. Supporting information Table S1.
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Chapitre III Unprecedented Tetranuc
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Abstract Chapitre III Reactions of
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Chapitre III distorted octahedral c
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data for 2a⋅2CH2Cl2: 1.41 and for
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Chapitre III indicate that subtle d
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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
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Chapitre III [S-5] J. K. McCusker,
Page 101 and 102: Abstract Chapitre IV The P,N-type l
Page 103 and 104: Chapitre IV Scheme 1. Complexes wit
Page 105 and 106: 12 PPh 2 N O N PPh 2 O N 13 P 14 15
Page 107 and 108: Chapitre IV Although some nickel co
Page 109 and 110: Scheme 2. Representation of the squ
Page 111 and 112: Chapitre IV The analysis of the dif
Page 113 and 114: Chapitre IV Table 4. Catalytic Data
Page 115 and 116: mass % of 1-butene 100 90 80 70 60
Page 117 and 118: Chapitre IV Table 6. Catalytic Data
Page 119 and 120: ef Scheme 3. Proposed pathways to e
Page 121 and 122: 4. Conclusion Chapitre IV New P,N l
Page 123 and 124: Chapitre IV SiCH3), 30.25 (s, SiCH2
Page 125 and 126: Chapitre IV 122.3 (s, Py), 122.5 (d
Page 127 and 128: [Ni(µ-Cl)2{(pyridin-2-yl) methanol
Page 129 and 130: Chapitre IV mmol of Ni complex or 1
Page 131 and 132: 6. References (1) Ziegler, K.; Holz
Page 133 and 134: Chapitre IV (44) Bluhm, M. E.; Foll
Page 135 and 136: Chapitre V Synthesis and catalytic
Page 137 and 138: Chapitre V to 16, the IR spectrum o
Page 139 and 140: Chapitre V activated by MAO (Scheme
Page 141 and 142: 2 OH N + PPhCl 2 NEt 3 - (HNEt 3)Cl
Page 143 and 144: Chapitre V Slow diffusion of heptan
Page 145 and 146: Chapitre V Figure 3. ORTEP view of
Page 147 and 148: Chapitre V tridentate ligand but wi
Page 149 and 150: Chapitre V spin system 1) and 3.06
Page 151: Chapitre V This establishes the coo
Page 155 and 156: % mass of 1-butene 80 70 60 50 40 3
Page 157 and 158: Chapitre V cyclic voltammograms of
Page 159 and 160: Chapitre V A n-BuLi solution (64.0
Page 161 and 162: Chapitre V IR (KBr): 1658 (vs), 147
Page 163 and 164: Chapitre V To a solution of (2-oxaz
Page 165 and 166: Chapitre V Synthesis of [Co{bis(1-(
Page 167 and 168: Chapitre V 30 bar working pressure
Page 169 and 170: 6. References 1 2 3 4 5 6 7 8 9 10
Page 171 and 172: 67 68 69 70 71 72 73 74 75 76 77 78
Page 173 and 174: Abstract Chapitre VI The β-keto ph
Page 175 and 176: Ph O 3 toluene PPh3 + Ni(COD) 2 + P
Page 177 and 178: Chapitre VI The synthesis of β-ket
Page 179 and 180: Table 1 Selected bond distances (Å
Page 181 and 182: Ph O toluene PR2R' + Ni(COD) 2 + C5
Page 183 and 184: 4. Conclusion Chapitre VI The β-ke
Page 185 and 186: Chapitre VI and the solution was st
Page 187 and 188: Chapitre VI (s, p-C of OC-Ph), 131.
Page 189 and 190: Chapitre VI To a solution of 13.000
Page 191 and 192: Chapitre VI the solvents under redu
Page 193 and 194: Chapitre VI Crystal Structure Deter
Page 195 and 196: 23 F. A. Hicks and M. Brookhart, Or
Page 197 and 198: Chapitre VII Réarrangement type Ar
Page 199 and 200: 1. Introduction Chapitre VII Brookh
Page 201 and 202: 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
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Chapitre II Résumé et conclusion
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Résumé et conclusion générale P
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Résumé et conclusion générale l
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Chapitre VII Résumé et conclusion
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Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

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