Olefin Upgrading Catalysis by Nitrogen-based Metal Complexes II Stat
Olefin Upgrading Catalysis by Nitrogen-based Metal Complexes II: State of the art and Perspectives provides a critical review of the state-of-the-art developments in industrially relevant processes connected to efficient and selective olefin upgrading. Sp
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Development of Imine Derivative Ligands for the Exocyclic Activation of Late Transition Metal Polymerization Catalysts Brian C. Peoples and René S. Rojas
Abstract Transition metal complexes bearing imine and imine derivative ligands represent a growing number of polymerization catalysts in development. The ease of synthesis and large number of structural variations which are readily accessible make these systems of great interest both academically and industrially. One subset of imine-based complexes are those which bear exocyclic functionality which can interact with Lewis acids. These systems are particularly interesting as the activation of the complex occurs remotely, away from the active center, and that the activation can proceed using stoichiometric concentrations of activators. In addition, the presence of the exocyclic functionality may present an effective method to heterogenize polymerization catalysts. In this chapter, the development of such systems and in particular a-iminocarboxamide nickel catalysts and derivative species are discussed. Abbreviations Acac Ar ArF B BCF
Acetylacetone Aryl Aryl group containing fluoro-atoms Lewis base Tris(pentafluorophenyl)borane
B. C. Peoples Departamento de Ingeniería Química, Centro para la Investigación Interdisciplinaria Avanzada en Ciencias de los Materiales (CIMAT), Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Santiago, Chile e-mail: [email protected] R. S. Rojas (&) Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago, Chile e-mail: [email protected]
G. Giambastiani and J. Cámpora (eds.), Olefin Upgrading Catalysis by Nitrogen-based Metal Complexes II, Catalysis by Metal Complexes, 36, DOI: 10.1007/978-94-007-0696-5_2, Ó Springer Science+Business Media B.V. 2011
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bipy Bz Cn COD Dipp dme en Et Ln Ls Lut M MAO Me NacNacH Px Ph Py r.t. THF Ts-CN tmeda X Y Z\Z0
B. C. Peoples and R. S. Rojas
2,20 -Bipyridyl Benzyl Complex 1,5-Cyclooctadiene Diisopropylphenyl Dimetoxiethane (ethylene glycol dimethylether) 1,2-Diaminoethane Ethyl Ligand Ligand salt Lutidine (2,6-dimethyl pyridine) Metal Methylaluminoxane Methyl 1,3-Diketimines Metal precursor Phenyl Pyridine Room temperature Tetrahydrofuran Para-toluenesulfonylcyanide N,N,N0 ,N0 -tetramethylethylenediamine Halogen or other anionic group Alkyl or functional groups Bidentate ligand (where Z is the coordinating atom)
2.1 Introduction Olefins can be upgraded to higher value products through a number of industrial processes, two of the most prevalent are the oligomerization of olefins to higher alkanes and the production of polyolefins via transition metal catalysis. Polyolefin production has grown in step with the development of the global economy and is expected to continue with time [1]. These materials are desirable for many reasons, including their low cost and the ease of which they can be shaped into many forms and sizes. Since the development of the first Ziegler-Natta (1953–1954) and Phillips catalysts (late 194
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