"Decarbonization" of an imino N-heterocyclic carbene via triple benzyl migration from hafnium

Authors: PREMA, DIPESH - Oklahoma State University; MATHOTA ARACHCHIGE, YOHAN - Oklahoma State University; Murray, Rex; SLAUGHTER, LE GRANDE - Oklahoma State University

Submitted to: ChemComm
Publication Type: Peer Reviewed Journal
Publication Acceptance Date: 3/13/2015
Publication Date: 4/9/2015
Publication URL: http://handle.nal.usda.gov/10113/62939
Citation: Prema, D., Mathota Arachchige, Y.L.N., Murray, R.E., Slaughter, L. 2015. Decarbonization of an imino N-heterocyclic carbene via triple benzyl migration from hafnium. ChemComm. 51(13):6753-6756.

Interpretive Summary: Polyethylene is the largest manufactured plastic with a global production of about 80 million tons per year. The consumer often purchases it in the form of plastic films and milk bottles. Catalysts are required to manufacture polyethylene from ethylene. The role of the catalyst is to connect thousands of ethylene molecules together, similar to how paper clips can be hooked together to create a long chain. A novel catalyst useful for the production of polyethylene is reported. As some bio-based polyethylene is now commercially manufactured from bio-based ethylene, this new catalyst discovery is potentially a tool for creating bio-based polyethylene. Bio-based polyethylene benefits agriculture because the bio-ethylene feedstock comes from fermentation products instead of petroleum.

Technical Abstract: An imino N-heterocyclic carbene underwent three sequential benzyl migrations upon reaction with tetrabenzylhafnium, resulting in complete removal of the carbene carbon from the ligand. The resulting eneamido-amidinato hafnium complex showed alkene polymerization activity comparable to that of a precatalyst containing the intact iminocarbene ligand.