The molecular-level effect of alkoxide additives in iron-catalyzed Kumada cross-coupling with simple ferric salts

The molecular-level role of alkoxide salts, used as alternative additive to N -methylpyrrolidone in iron-catalyzed alkyl-alkenyl/aryl cross-coupling reactions, is investigated. Detailed spectroscopic studies reveal that alkoxides promote the formation of homoleptic organoferrates such as [FeMe 3 ] − , providing an alternative to toxic NMP to access these reactive intermediates. Alkoxide additives promote the formation of low-coordinate homoleptic iron( ii ) intermediates in cross-coupling reactions with simple iron salts.