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Updated: Jul 10, 2026

Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
Published on: November 27, 2015
Complicated goings-on in the metal-manipulated ring-opening of cyclobutene
1Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853-1301, USA.
Abstract:
Most reported examples of transition metal-mediated pericyclic reactions have been shown to proceed by nonpericyclic mechanisms. However, the conversion of Fe(CO)(4)-cyclobutenes to Fe(CO)(3)-butadienes and CO is thought to proceed through a mechanism involving an electrocyclic ring-opening step. We have examined this and possible alternative mechanisms for the parent Fe(CO)(4)-cyclobutene complex using hybrid HF-DFT calculations. In this system there is an inherent preference for a pathway that avoids metal-templated electrocyclic ring-opening, but the pericyclic pathway is predicted to dominate for more elaborate substrates and under certain experimental conditions.
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