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1	New calix[4]arene metal complexes Dubberley, Stuart R. January 2000 (has links) No description available. 546 Anionic; Ligands
2	Greffage de complexes organométalliques sur anions hydroxyborates : application à la transformation des oléfines / The use of hydroxyborate anions as anchors for organometallic complexes : application to olefin transformation reactions Kelsen, Vinciane 14 December 2010 (has links) Cette thèse présente le greffage de complexes organométalliques sur des anions hydroxyborates. Ces ligands originaux sont susceptibles de conférer des propriétés particulières à la sphère de coordination du métal. Leur caractère anionique pourrait permettre l'immobilisation des catalyseurs dans une phase liquide ionique. La majeure partie des travaux a porté sur la réactivité des anions hydroxyborates avec les métaux du groupe IV de la classification périodique. Les complexes alkyles du zirconium et de l'hafnium réagissent avec la fonction hydroxyle de l'anion par protonolyse de la liaison métal-alkyle. La résolution par diffraction des rayons X de la structure des complexes métallocènes [Cp2MMe(OB(C6F5)3)]- [PPN]+ (M = Zr et Hf) a confirmé la nature covalente des liaisons M-O et B-O et donc l'intérêt des anions hydroxyborates comme ligands de complexes organométalliques. Cette réactivité a ensuite été déclinée sur différents précurseurs du zirconium et de l'hafnium. Le complexe ionique [Ti(OiPr)3(OB(C6F5)3]-[PPN]+ a été synthétisé à partir d'un complexe alkoxy du titane par une réaction d'échange de ligands. Ce complexe activé par le triéthylaluminium dimérise sélectivement l'éthylène en butène-1 en milieu liquide ionique. L'extension du concept à d'autres métaux de la classification périodique : aluminium, fer, molybdène, a été abordée. Deux complexes anioniques du molybdène ont notamment été isolés et sont des catalyseurs de métathèse des oléfines / This thesis presents the use of hydroxyborate anions as anchors for organometallic complexes. These original ligands might confer particular properties to the coordination sphere of the metal. Their anionic nature might also allow the immobilization of catalysts in ionic liquids. The main part of this work dealt with the reactivity of hydroxyborate anions with group IV metals. Zirconium and hafnium complexes reacted with the hydroxyl function of the anion by protonolysis of the metal-alkyl bond. Resolution of the structure of metallocene complexes [Cp2MMe(OB(C6F5)3)]-[PPN]+ (M = Zr and Hf) by X-Ray diffraction confirmed the covalent nature of M-O and B-O bonds and so the relevance of hydroxyborate anions as ligands for organometallic complexes. Then, this reactivity was extended to different zirconium and hafnium precursors. The ionic complex [Ti(OiPr)3(OB(C6F5)3)]- [PPN]+ was synthesized from an alkoxy titanium complex by a ligand exchange reaction. This complex activated by triethylaluminium selectively dimerized ethylene into 1-butene in ionic liquids. Extension of the concept to other metals such as aluminum, iron and molybdenum, was studied. Two anionic molybdenum complexes were isolated and are catalysts for olefin metathesis Anions hydroxyborates Ligands anioniques Catalyse biphasique Oligomérisation Métathèse Oléfines Complexes organométalliques Hydroxyborate anions Anionic ligands Biphasic catalysis Oligomerization Metathesis Olefins Organometallic complexes 547
3	Investigations into cyclopropanation and ethylene polymerization via salicylaldiminato copper (II) complexes Boyd, Ramon Cornell 23 January 2007 Two distinct overall research objectives are in this Masters thesis. Very little relates the two chapters apart from the ligands. The first chapter addresses diastereoselective homogeneous copper catalyzed cyclopropanation reactions. Cyclopropanation of styrene and ethyl diazoacetate (EDA) is a standard test reaction for homogeneous catalysts. Sterically bulky salicylaldimine (SAL) ligands should select for the ethyl trans-2-phenylcyclopropanecarboxylate diastereomer. Steric bulk poorly influences trans:cis ratios. Salicylaldiminine ligands do not posses the correct symmetry to affect diastereoselectivity. The SAL ligand belongs to the Cs point group in the solid state. Other ligand motifs are more effective at altering the trans:cis ratios. The second chapter addresses the general route toward successful copper(II) ethylene polymerization catalysts. Catalytic activity of the copper(II) complexes is very low. Polymer chain growth from a copper catalyst is very unlikely. Copper-carbon bonds decompose by homolytic cleavage or C-H activation. Copper-alkyls and aryls readily decompose into brown colored oils and salts with different colors. Ligand transfer to trimethylaluminum (TMA) appears to explain low yield ethylene polymerization. bulky migratory insertion mechanism coordination/insertion methodology d-block metal late transition metal phenolic ring coordination number ketimine precatalysts ketimine nitrogen bis(salicylaldiminato)copper(II) ratio cyclopropane steric bulk salicylaldiminato TMA salt trimethylaluminum aryl oil alkyl copper-aryls copper-alkyls C-H activation homolytic homolytic cleavage copper(II) polymerization ethylene cis trans symmetry diastereomer salicylaldimine SAL EDA ethyl diazoacetate styrene cyclopropanation copper diastereoselective steric protection stable CH(SiMe3)2 intermediate catalytic activity associated TMA free TMA vacant coordination site hydrolysis Lewis acid halogen anionic anionic ligand donor ligand monodentate anionic ligand aluminum(III) monodentate polymer chain polymer chain aluminum-carbon bond bulky SAL ligand open coordination site first row transition metal PE paramagnetic high molecular weight polyethylene alkylate methylaluminoxane MAO anionic ligands arylate aluminum carbon aluminum carbon bond beta-hydrogen elimination beta hydrogen elimination Aufbau reaction Aufbau neutral dialkyl aluminum aluminum-alkyl aluminum alkyl copper(0)
4	Investigations into cyclopropanation and ethylene polymerization via salicylaldiminato copper (II) complexes Boyd, Ramon Cornell 23 January 2007 (has links) Two distinct overall research objectives are in this Masters thesis. Very little relates the two chapters apart from the ligands. The first chapter addresses diastereoselective homogeneous copper catalyzed cyclopropanation reactions. Cyclopropanation of styrene and ethyl diazoacetate (EDA) is a standard test reaction for homogeneous catalysts. Sterically bulky salicylaldimine (SAL) ligands should select for the ethyl trans-2-phenylcyclopropanecarboxylate diastereomer. Steric bulk poorly influences trans:cis ratios. Salicylaldiminine ligands do not posses the correct symmetry to affect diastereoselectivity. The SAL ligand belongs to the Cs point group in the solid state. Other ligand motifs are more effective at altering the trans:cis ratios. The second chapter addresses the general route toward successful copper(II) ethylene polymerization catalysts. Catalytic activity of the copper(II) complexes is very low. Polymer chain growth from a copper catalyst is very unlikely. Copper-carbon bonds decompose by homolytic cleavage or C-H activation. Copper-alkyls and aryls readily decompose into brown colored oils and salts with different colors. Ligand transfer to trimethylaluminum (TMA) appears to explain low yield ethylene polymerization. bulky migratory insertion mechanism coordination/insertion methodology d-block metal late transition metal phenolic ring coordination number ketimine precatalysts ketimine nitrogen bis(salicylaldiminato)copper(II) ratio cyclopropane steric bulk salicylaldiminato TMA salt trimethylaluminum aryl oil alkyl copper-aryls copper-alkyls C-H activation homolytic homolytic cleavage copper(II) polymerization ethylene cis trans symmetry diastereomer salicylaldimine SAL EDA ethyl diazoacetate styrene cyclopropanation copper diastereoselective steric protection stable CH(SiMe3)2 intermediate catalytic activity associated TMA free TMA vacant coordination site hydrolysis Lewis acid halogen anionic anionic ligand donor ligand monodentate anionic ligand aluminum(III) monodentate polymer chain polymer chain aluminum-carbon bond bulky SAL ligand open coordination site first row transition metal PE paramagnetic high molecular weight polyethylene alkylate methylaluminoxane MAO anionic ligands arylate aluminum carbon aluminum carbon bond beta-hydrogen elimination beta hydrogen elimination Aufbau reaction Aufbau neutral dialkyl aluminum aluminum-alkyl aluminum alkyl copper(0)

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