Over the past decade, advances in ethylene oligomerization have witnessed explosive growth of interest from both commercial and academic standpoint, with chromium metal invariably being the metal of preference. A common feature in this literature was the extended long debate regarding the mechanism, metal oxidation states responsible for selectivity and the role of the ligand. This thesis work embarked on the isolation and characterization of new active intermediates called “single component catalysts” (or self activating) to address two important questions: (1) how the catalyst precursors re-arrange upon activation and (2) the real oxidation state of the activated species. Four different ligands systems have been examined for this purpose. The first part is a study on the NPIIIN ligand which can be described as a dynamic and non-spectator ligand. Upon aluminum alkyl activation, a series of single component chromium catalysts for selective ethylene oligomerization and polymerization have been isolated, fully characterized and tested. New selective single component chromium(I) catalysts have also been isolated and tested positively for ethylene trimerization. The second part includes a new series of chromium complexes based on the NPVN ligand. This ligands enabled to obtain the first polymer-free extremely active catalytic system. In both NPN ligand systems, a new activation pathway was discovered by using vinyl Grignard reagent [(CH2=CH)MgCl] as activator and/or reducing agent. The third part explores new modified pyrrole-chromium complexes which were found to be highly active and selective ethylene trimerization catalysts. This part was a continuation of previous work from our lab to complete the mechanistic picture of this highly successful pyrrole-chromium catalyst independently commercialized by Phillips-Chevron and Mitsubishi. Interestingly upon aluminum alkyl treatment, the first example of a Schrock-type chromium ethylidene complex has been isolated and characterized and found to be a potent catalyst for selective ethylene trimerization. Finally, the other ligands introduced in this thesis are new systems called pyridine-SNS and Si-SNS that introduce some modification to the known commercial SNS catalyst (Sasol technology). The introduction of a pyridine ring or a silyl unit in the ligand scaffold has allowed to understand the mechanism of action of this remarkable system.

Over the past decade, advances in ethylene oligomerization have witnessed explosive growth of interest from both commercial and academic standpoint, with chromium metal invariably being the metal of preference. A common feature in this literature was the extended long debate regarding the mechanism, metal oxidation states responsible for selectivity and the role of the ligand. This thesis work embarked on the isolation and characterization of new active intermediates called “single component catalysts” (or self activating) to address two important questions: (1) how the catalyst precursors re-arrange upon activation and (2) the real oxidation state of the activated species. Four different ligands systems have been examined for this purpose. The first part is a study on the NPIIIN ligand which can be described as a dynamic and non-spectator ligand. Upon aluminum alkyl activation, a series of single component chromium catalysts for selective ethylene oligomerization and polymerization have been isolated, fully characterized and tested. New selective single component chromium(I) catalysts have also been isolated and tested positively for ethylene trimerization. The second part includes a new series of chromium complexes based on the NPVN ligand. This ligands enabled to obtain the first polymer-free extremely active catalytic system. In both NPN ligand systems, a new activation pathway was discovered by using vinyl Grignard reagent [(CH2=CH)MgCl] as activator and/or reducing agent. The third part explores new modified pyrrole-chromium complexes which were found to be highly active and selective ethylene trimerization catalysts. This part was a continuation of previous work from our lab to complete the mechanistic picture of this highly successful pyrrole-chromium catalyst independently commercialized by Phillips-Chevron and Mitsubishi. Interestingly upon aluminum alkyl treatment, the first example of a Schrock-type chromium ethylidene complex has been isolated and characterized and found to be a potent catalyst for selective ethylene trimerization. Finally, the other ligands introduced in this thesis are new systems called pyridine-SNS and Si-SNS that introduce some modification to the known commercial SNS catalyst (Sasol technology). The introduction of a pyridine ring or a silyl unit in the ligand scaffold has allowed to understand the mechanism of action of this remarkable system.

Over the past decade, advances in ethylene oligomerization have witnessed explosive growth of interest from both commercial and academic standpoint, with chromium metal invariably being the metal of preference. A common feature in this literature was the extended long debate regarding the mechanism, metal oxidation states responsible for selectivity and the role of the ligand. This thesis work embarked on the isolation and characterization of new active intermediates called “single component catalysts” (or self activating) to address two important questions: (1) how the catalyst precursors re-arrange upon activation and (2) the real oxidation state of the activated species. Four different ligands systems have been examined for this purpose. The first part is a study on the NPIIIN ligand which can be described as a dynamic and non-spectator ligand. Upon aluminum alkyl activation, a series of single component chromium catalysts for selective ethylene oligomerization and polymerization have been isolated, fully characterized and tested. New selective single component chromium(I) catalysts have also been isolated and tested positively for ethylene trimerization. The second part includes a new series of chromium complexes based on the NPVN ligand. This ligands enabled to obtain the first polymer-free extremely active catalytic system. In both NPN ligand systems, a new activation pathway was discovered by using vinyl Grignard reagent [(CH2=CH)MgCl] as activator and/or reducing agent. The third part explores new modified pyrrole-chromium complexes which were found to be highly active and selective ethylene trimerization catalysts. This part was a continuation of previous work from our lab to complete the mechanistic picture of this highly successful pyrrole-chromium catalyst independently commercialized by Phillips-Chevron and Mitsubishi. Interestingly upon aluminum alkyl treatment, the first example of a Schrock-type chromium ethylidene complex has been isolated and characterized and found to be a potent catalyst for selective ethylene trimerization. Finally, the other ligands introduced in this thesis are new systems called pyridine-SNS and Si-SNS that introduce some modification to the known commercial SNS catalyst (Sasol technology). The introduction of a pyridine ring or a silyl unit in the ligand scaffold has allowed to understand the mechanism of action of this remarkable system.

Over the past decade, advances in ethylene oligomerization have witnessed explosive growth of interest from both commercial and academic standpoint, with chromium metal invariably being the metal of preference. A common feature in this literature was the extended long debate regarding the mechanism, metal oxidation states responsible for selectivity and the role of the ligand. This thesis work embarked on the isolation and characterization of new active intermediates called “single component catalysts” (or self activating) to address two important questions: (1) how the catalyst precursors re-arrange upon activation and (2) the real oxidation state of the activated species. Four different ligands systems have been examined for this purpose. The first part is a study on the NPIIIN ligand which can be described as a dynamic and non-spectator ligand. Upon aluminum alkyl activation, a series of single component chromium catalysts for selective ethylene oligomerization and polymerization have been isolated, fully characterized and tested. New selective single component chromium(I) catalysts have also been isolated and tested positively for ethylene trimerization. The second part includes a new series of chromium complexes based on the NPVN ligand. This ligands enabled to obtain the first polymer-free extremely active catalytic system. In both NPN ligand systems, a new activation pathway was discovered by using vinyl Grignard reagent [(CH2=CH)MgCl] as activator and/or reducing agent. The third part explores new modified pyrrole-chromium complexes which were found to be highly active and selective ethylene trimerization catalysts. This part was a continuation of previous work from our lab to complete the mechanistic picture of this highly successful pyrrole-chromium catalyst independently commercialized by Phillips-Chevron and Mitsubishi. Interestingly upon aluminum alkyl treatment, the first example of a Schrock-type chromium ethylidene complex has been isolated and characterized and found to be a potent catalyst for selective ethylene trimerization. Finally, the other ligands introduced in this thesis are new systems called pyridine-SNS and Si-SNS that introduce some modification to the known commercial SNS catalyst (Sasol technology). The introduction of a pyridine ring or a silyl unit in the ligand scaffold has allowed to understand the mechanism of action of this remarkable system.

Dans cette thèse nous avons eu pour but d’étudier la réactivité des complexes à bas degré d’oxydation du fer stabilisés par des ligands phosphines vis-à-vis des substrats insaturés. Cet objectif s’inscrit dans une démarche plus large d’accès à des systèmes catalytiques au fer capables de transformer de manière sélective l’éthylène, par la réaction d’oligomérisation, vers des alpha-oléfines linéaires courtes (butène-1, héxène-1, octène-1), ce qui n’a jamais été rapporté dans la littérature. Pour se faire, le passage par le mécanisme métallacyclique de transformation de l’éthylène est la voie privilégiée. Cependant, les propriétés électroniques et géométriques de ligand requises pour suivre un tel mécanisme, et en particulier son étape clé de couplage oxydant de deux molécules d’éthylène sur le centre métallique, ne sont pas clairement identifiées. Nous rapportons ici dans un premier temps la synthèse d’une bibliothèque de complexes de fer(II) et fer(III) à base de ligands phosphines présentant des propriétés électroniques et géométriques variées. Ces nouveaux complexes sont opportunément testés en tant que catalyseurs, d’une part pour la réaction d’oligomérisation de l’éthylène; mais également en tant qu’espèces réduites in situ en association avec des diènes (isoprène, butadiène) conduisant à leur polymérisation. Afin de nous rapprocher davantage de notre objectif d’accès aux espèces à bas degré d’oxydation du fer, l’emploi d’une voie de réduction en une étape et en conditions douces est rapportée; conduisant à l’isolement et la caractérisation de neuf complexes phosphorés de fer(0) à 18 et à 16 électrons. Bien qu’a priori inactifs vis-à-vis de l’éthylène ou des oléfines plus longues, nous montrons la capacité de ces complexes à promouvoir des réactions de couplage oxydant de substrats insaturés (alcynes) le couplage catalytique de l’éthylène et du butadiène et l’activation de divers composés tels que les silanes ou les halogénures d’alkyles, posant ainsi un premier jalon vers leur optimisation et application en tant que catalyseurs d’autres réactions, et potentiellement dans l’avenir, pour la transformation de l’éthylène. / In this thesis our aim was to study the reactivity of phosphine-based low-valent iron complexes towards unsaturated substrates. This goal is part of a wider approach of access to an iron catalytic system able to transform ethylene in a selective manner, by the reaction of oligomerization, towards short linear alpha-olefins (1-butene, 1-hexene, 1-octene), which is unreported in the literature. To achieve this, going through the metallacyclic mechanism of ethylene transformation is the most likely way. However, the electronic and geometrical features of the ligand required to follow this mechanism, and in particular the key step of the oxidative coupling of two molecules of ethylene to the metal center, are ill-defined. We thus report here in a first part the synthesis of a library of P-based iron(II) and iron(III) complexes bearing varied electronic and geometrical features. These novel complexes are opportunistically screened as catalysts for ethylene oligomerization on one hand, and as in situ reduced species in association with dienes (isoprene, butadiene) leading to the polymerization of the latter substrates, on the other hand. In order to get closer to our goal of access to low-valent iron complexes, the use of a one-pot reduction methodology under mild conditions is reported, leading to the isolation and characterization of nine 18- and 16-electron iron(0) complexes. Even though they do not show reactivity towards ethylene or longer olefins, we demonstrate the ability of these complexes to promote reactions involving the oxidative coupling elementary step of unsaturated substrates (alkynes), the catalytic coupling of ethylene and butadiene and the activation of various compounds such as silanes and organic halides, representing a first milestone towards their optimization and application as catalysts for other reactions, including potentially in the near future, for ethylene transformation