Synthesis, Characterization and Catalytic Activity of Chromium Complexes

Abstract

There has been a growing demand for specific linear alpha olefins in the polyethylene industry in order to control polymer rheology. This growing demand thereby increases the need for highly active and selective ethylene oligomerization catalysts. Chromium-based catalysts continue to be of high interest for this application due to this metal’s versatility in both selective and non selective ethylene oligomerization. Ligand design is an important consideration in oligomerization chemistry: the ability of the ligand to stabilize low valent chromium and to support a two-electron redox process will allow the catalytic systems to follow the selective ring expansion mechanism for oligomerization. Chelating aminophosphane based ligands, previously studied by our group, have been shown to support both tri- and tetramerization of ethylene. We have explored modifications of one of the NP arms by replacing with a different coordinating group in an attempt to further stabilize the monovalent state of chromium and increase selectivity. Other ligands explored in this work are pyrrole based ligands, which have shown high activity and selectivity towards ethylene oligomerization. One example of this is the commercial Chevron-Phillips system. Recently, the co-polymerization of CO2 with epoxides has been studied as an environmentally friendly route to convert CO2 into biodegradable polymers. The first successful catalytic system to achieve these results consisted of a diethyl-zinc complex. More recently, aluminum, chromium, cadmium and cobalt have been studied as polycarbonate catalysts. To date, the only reported chromium catalysts for CO2-epoxide copolymerization are Cr-salen and Cr-porphyrin complexes, studied by Darrensbourg and Holmes, respectively. We were particularly interested in finding new chromium-based complexes able to catalyze epoxide/CO2 copolymerization by using molecules with the nitrogen donor motif embedded in different functions such as neutral pyridines with anionic pendants, pyrroles with either imine or amine pendants, or a combination of these.