Ligand Field Sensitive Spin Acceleration in the Iron-Catalyzed [2 + 2] Cycloaddition of Unactivated Alkenes and Dienes.

Redox-active pyridine(diimine) (PDI) iron catalysts promote the reversible [2 + 2] cycloaddition of alkenes and dienes to cyclobutane derivatives that have applications ranging from fuels to chemically recyclable polymers. Metallacycles were identified as key intermediates, and spin crossover from the singlet to the triplet surface was calculated to facilitate the reductive coupling step responsible for the formation of the four-membered ring. In this work, a series of sterically and electronically differentiated PDI ligands was studied for the [2 + 2] cycloaddition of ethylene and butadiene to vinylcyclobutane.

Bimolecular Reductive Elimination of Ethane from Pyridine(diimine) Iron Methyl Complexes: Mechanism, Electronic Structure, and Entry into [2+2] Cycloaddition Catalysis.

The application of bimolecular reductive elimination to the activation of iron catalysts for alkene-diene cycloaddition is described. Key to this approach was the synthesis, characterization, electronic structure determination, and ultimately solution stability of a family of pyridine(diimine) iron methyl complexes with diverse steric properties and electronic ground states. Both the aryl-substituted, (PDI)FeCH and (PDI)FeCH (PDI = 2,6-(2,6-R-CHN═CMe)CHN), and the alkyl-substituted examples, (APDI)FeCH (APDI = 2,6-(CHN═CMe)CHN), have molecular structures significantly distorted from planarity and = 3/2 ground states.

Iron-Catalyzed Vinylsilane Dimerization and Cross-Cycloadditions with 1,3-Dienes: Probing the Origins of Chemo- and Regioselectivity.

The selective, intermolecular, homodimerization and cross-cycloaddition of vinylsilanes with unbiased 1,3-dienes, catalyzed by a pyridine-2,6-diimine (PDI) iron complex is described. In the absence of a diene coupling partner, vinylsilane hydroalkenylation products were obtained chemoselectively with unusual regioselectivity (up to >98% purity, 98:2 ). In the presence of a 4- or 2-substituted diene coupling partner, under otherwise identical reaction conditions, formation of value-added [2+2]- and [4+2]-cycloadducts, respectively, was observed.