Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

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Chapitre V Table 6. Comparative Catalytic Data for Complexes 6, 8 and 9 in the Oligomerization of Ethylene a, b with MAO as Cocatalyst. MAO Selectivity (mass %) (equiv) C4 C6 C8 Productivity [g C2H4/(g Ni·h)] TOF [mol C2H4/(mol Ni·h)] α-olefin (C4) (mol %) 6 100 71 26 3 3900 9300 24 0.24 6 200 69 25 6 5800 12200 24 0.24 8 200 91 8
% mass of 1-butene 80 70 60 50 40 30 20 10 0 100 Equiv of MAO 200 400 6 8 9 Chapitre V Figure 11. Selectivity of the complexes 6, 8 and 9 for 1-butene using MAO as cocatalyst. . % mass of C4 oleifns 100 90 80 70 60 50 40 30 20 10 0 100 Equiv of MAO 200 400 Figure 12. Selectivity of the complexes 6, 8 and 9 for C4 compounds using MAO as cocatalyst (1-butene and 2-butene). Different concentrations of complex 16 (10 -5 or 4·10 -5 mol of complex dissolved in a total volume of 15 ml) have been tested in ethylene oligomerization with 6 and 12 equiv of AlEtCl2 (Table 7). In both cases, the complex presented modest activities but high selectivities for the dimerization of ethylene into 1-butene with AlEtCl2 as cocatalyst. To obtain better activities, we heated the catalytic solution at 80 °C and increased the ethylene pressure to 30 bar. Under these conditions, the TOF was up to 17700 mol C2H4/(mol Co·h) and the system remained selective in C4 olefins (97%) but the isomerization increased and the selectivity in 1-butene was 48%. With MAO as cocatalyst, 16 did not present any significant catalytic activity. 6 8 9 21
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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,
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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 and 152: Chapitre V This establishes the coo
Page 153: TOF (mol C2H4/(mol Ni.h)) 90000 800
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
Page 203 and 204: 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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